CN107540635B - A kind of anti-hardened dazomet preparation method - Google Patents
A kind of anti-hardened dazomet preparation method Download PDFInfo
- Publication number
- CN107540635B CN107540635B CN201710938723.XA CN201710938723A CN107540635B CN 107540635 B CN107540635 B CN 107540635B CN 201710938723 A CN201710938723 A CN 201710938723A CN 107540635 B CN107540635 B CN 107540635B
- Authority
- CN
- China
- Prior art keywords
- dazomet
- phosphate
- hardened
- solution
- carbon disulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fertilizers (AREA)
Abstract
The present invention relates to a kind of anti-hardened dazomet preparation methods, belong to pesticide synthesis technical field.In order to solve the problems, such as short easy caking of existing resting period, a kind of anti-hardened dazomet preparation method is provided, this method is included in addition permanganate water solution in carbon disulfide solution and is pre-processed, is layered, collects the carbon disulfide solution by pretreatment；The carbon disulfide solution of pretreatment with dense methylamine water solution is reacted, obtains the aqueous solution containing N methyl aminodithioformic acids；In the presence of phosphate, amphoteric surfactant and EDTA, reacted with formaldehyde, obtain dazomet；Phosphate addition is the 1.0%~1.5% of the quality of formaldehyde, the phosphate：Amophoteric surface active：The mass ratio of EDTA is 1：0.5~0.6：0.01~0.02.The present invention can increase the uniformity of particle and be distributed concentration degree and increase the anti-compaction of dazomet particle, so that the effect with high fluidity.
Description
Technical field
The present invention relates to a kind of anti-hardened dazomet preparation methods, belong to pesticide synthesis technical field.
Background technology
Dazomet is a kind of less toxic wide spectrum fumigating nematicide, simultaneous can control soil fungi, subterranean pest-insect and weeds.It is being applied to
In wetland environment, it can decompose to seek a quarrel and be diffused between soil particle, it is effective to kill various nematodes, pathogen in soil
And weed seed etc., so as to reach clean effect, and with long efficacy time is relatively held, apply also for prevention vegetables, strawberry
Various nematodes Deng on.Dazomet is typically processed into the dosage forms such as pulvis, wettable powder.
At present, carbon disulfide, monomethyl amine and formaldehyde are mainly used to be main former for the production method of dazomet both at home and abroad
Material, is reacted by two steps, is specially：First passing through makes carbon disulfide and the methylamine solution reaction generation N- methyl two after dilution
Thiocarbamic acid；Auxiliary agent is added, and formalin is added dropwise and is reacted, obtains final product dazomet.But current side
Method, which is generally present with during storage, the hardened phenomenons such as occurs luming, and grain thickness distribution is wide, is unfavorable for drug effect
It plays, meanwhile, dilute methylamine water solution after dilution is used, substantial amounts of waste water is also easy to produce, is unfavorable for environment.Such as Chinese patent Shen
Please (publication number：CN106831649A a kind of dazomet preparation process) is disclosed, by making methylamine with adding again after carbon disulfide reaction
Enter suitable extractant, separation obtains intermediate N methyl aminodithioformic acid, then is being with the addition of suitable sulfuric acid with formaldehyde
Reaction obtains dazomet in the reaction system of salt and surfactant.It is primarily to solve because carbon disulfide remnants are to product
The influence of crystal structure, regulation density and security, but also do not provide and how to solve the problems, such as that caking easily occurs in dazomet.
The content of the invention
The present invention provides a kind of anti-hardened dazomet preparation method, solves for above defect in the prior art
The problem of be that the product how to make has both high fluidity and the high performance of bulk density.
The purpose of the present invention is what is be achieved by the following technical programs, a kind of anti-hardened dazomet preparation method,
It is characterized in that, this method comprises the following steps：
A, permanganate water solution is added in carbon disulfide solution to be pre-processed, be layered, collect by pretreatment
Carbon disulfide solution；
B, reacted what step A was obtained by the carbon disulfide solution pre-processed with dense methylamine water solution, reaction knot
Shu Hou, layering remove oil phase, obtain the aqueous solution containing N- methyl aminodithioformic acids；The quality of the dense methylamine water solution
Concentration >=30%；
C, in the presence of phosphate, amphoteric surfactant and EDTA, make containing N- methyl aminodithioformic acids
Aqueous solution is reacted with formaldehyde, obtains dazomet；The phosphatic addition is the 1.0%~1.5% of the quality of formaldehyde, institute
State phosphate：Amophoteric surface active：The mass ratio of EDTA is 1：0.5~0.6：0.01~0.02.
The present invention is by first pre-processing carbon disulfide solution using permanganate, in order to remove curing
The impurity such as sulphur, hydrogen sulfide in carbon avoid these impurity and enter reaction system and form some by-products, remove unpleasant gas
Taste, and the present inventor is had found after permanganate is handled in the course of the research, and dazomet can be avoided to occur during storing
Knot tying phenomenon makes final product have good mobility；It and can be directly molten using dense methylamine after permanganate is handled
Liquid is reacted, and is needed not move through dilution processing, be greatly reduced waste water, avoid subsequent wastewater treatment and environmental pollution, also
Can play increases the effect of bulk density, and dense methylamine water solution generally refers to mass concentration more than more than 30%；Meanwhile pass through
The synergistic effect of phosphate, amphoteric surfactant and EDTA are added in, is concentrated so as to increase the uniformity of particle and distribution
Degree allows to effectively be distributed in the range of a relatively concentration, without making distribution excessively scattered, and is incorporated in permanganate
After pretreatment removes the impurity in carbon disulfide, allow to improve phosphate and the validity of EDTA avoids it because of carbon disulfide etc.
The presence of the impurity such as hydrogen sulfide and sulphur and lose anti-hardened performance, in addition, phosphatic addition is also a key here
Factor, if its excessive or very few anti-compaction added in can reduce instead.So that the association by adding in phosphate and EDTA
Under same-action, it can similarly increase the anti-compaction of dazomet particle, so that the effect with high fluidity.
In above-mentioned anti-hardened dazomet preparation method, preferably, the quality of dense methylamine water solution described in step B
Concentration is 35wt%~40wt%.Using the methylamine water solution of high concentration, reduce the generation of wastewater flow rate, and product can be improved
Bulk density.
In above-mentioned anti-hardened dazomet preparation method, preferably, phosphate described in step C be selected from potassium phosphate,
One or more of sodium phosphate, dibastic sodium phosphate or potassium hydrogen phosphate.Anti-compaction energy can be further improved, makes to have preferable
Mobility, meanwhile, using these phosphate can play improve bulk density effect.As it is further preferably, it is described
Phosphatic addition is the 1.0%~1.5% of the quality of formaldehyde.Preferably make phosphate：Amophoteric surface active：The quality of EDTA
Than for 1：0.5~0.6：0.01~0.02.Be conducive to play synergistic effect, enable that there is preferable mobility and anti-compaction,
Make to be less prone to caking phenomenon, the advantages of resting period is long.
In above-mentioned anti-hardened dazomet preparation method, preferably, step C is specially：
Phosphate, amphoteric surfactant and EDTA are added in reaction kettle, then adds formalin, control is anti-
Temperature≤30 DEG C of system are answered, then the aqueous solution containing N- methyl aminodithioformic acids is added dropwise, defoaming is added in during being added dropwise
Agent, after being added dropwise, making the pH value of reaction system, after reaction, crystallization filters, obtains dazomet 7.0~7.5.Passing through will
The aqueous solution of N- methyl aminodithioformic acids is added drop-wise in formaldehyde, is reduced because of the addition mistake of N- methyl aminodithioformic acids
Cause the generation of by-product greatly, in order to improve the content and yield of product.
In above-mentioned anti-hardened dazomet preparation method, preferably, containing two thio ammonia of N- methyl described in step B
Added with paraffin in the aqueous solution of base formic acid, the addition of the paraffin is 1wt%~2wt% of gross mass.Purpose be in order to
Hygroscopicity is reduced, prevents intermediate product from signs of degradation occur, reduces the generation of by-product；Meanwhile paraffin is added in, it is prior
It is the anti-compaction energy that can improve final product dazomet, avoids caking phenomenon occur during storage, improve the effect of mobility
Fruit.
In above-mentioned anti-hardened dazomet preparation method, preferably, permanganate described in step A is selected from permanganic acid
Sodium or potassium permanganate.Raw material is easy to get, and is conducive to remove the reducing impurities such as sulphur in carbon disulfide, makes to be more advantageous to improving product
Anti-compaction energy, the further effect for ensureing mobility.
In above-mentioned anti-hardened dazomet preparation method, preferably, amphoteric surfactant is selected from described in step C
One or more of carboxylic acid glycine betaine, sulphonic acid betaine and dodecyl ethyoxyl sulfobetaines.It is lived using amphoteric surface
Property agent can form preferable synergistic effect with phosphate and EDTA, enable to reach better anti-compaction.As further
It is preferred, the amphoteric surfactant is the mixture of carboxylic acid glycine betaine and dodecyl ethyoxyl sulfobetaines, and institute
The mass ratio for stating dodecyl ethyoxyl sulfobetaines and carboxylic acid glycine betaine is 1：0.2~0.5.It can make raising mobility
Meanwhile make the effect with preferable bulk density and centralized particle diameter degree.
In conclusion it compared with prior art, the present invention has the following advantages：
The present invention is pre-processed carbon disulfide by using permanganate and is directly carried out using dense methylamine solution anti-
The synergistic effect using phosphate, amphoteric surfactant and EDTA should and be combined, the uniformity of particle can be increased and is divided
Cloth concentration degree and the anti-compaction for increasing dazomet particle, so that the effect with high fluidity.
Specific embodiment
Below by specific embodiment, the technical solutions of the present invention will be further described, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1
1000g carbon disulfide is added in there-necked flask, then, it is molten that the potassium permanganate that 100mL mass concentrations are 2% is added dropwise
Liquid after being added dropwise, continues agitator treating 50min, then stands 30min, is layered, and removes water phase, collects two after washing
Vulcanize carbon solution, for reacting in next step.
Then, 700g monomethylamine aqueous solutions then in another new clean there-necked flask are added in, wherein, monomethylamine aqueous solution
Mass concentration for 35% (being equivalent to 245g methylamines (7.9mol)), control temperature exists<30 DEG C, above-mentioned carbon disulfide solution is added dropwise
300g (3.9mol) after dripping, when continuation insulation reaction 2 is small, after reaction, carries out standing 30 minutes, layering divides and goes down
The extra carbon disulfide (can cover and use next group) of layer, collects the aqueous solution containing N- methyl aminodithioformic acids and is directly used in
It reacts in next step；
The formalin (being equivalent to formaldehyde 8.0mol) that 600g mass concentrations are 40% is added in another reactor,
2.4g sodium phosphates, 1.2g amphoteric surfactant carboxylic acid glycine betaines and 0.03gEDTA, then, control Wen Du ≤30 DEG C start
The aqueous solution obtained above containing N- methyl aminodithioformic acids is added dropwise, about drips off when 5 is small or so, after dripping off, makes
7.5 or so, reaction terminates pH value of reaction system, then filters, and filter cake is washed with clear water, obtains final product cotton
It is grand.Obtained dazomet is subjected to relevant performance test, the results showed that, heap density is in 0.8g/cm3More than, content is 98.8%
More than, average grain diameter is 95 mesh, and the particle diameter distribution of particle, between -98 mesh of 90 mesh, concentration degree is good, yield 97.5%.
The centralized particle diameter degree of grain is high, and can realize during storage caking phenomenon (6 months resting periods or more) do not occur,
The good fluidity of product.As it can be seen that by advance permanganate being used to handle in the present embodiment, and make the addition of sodium phosphate for first
Aldehyde dosage 1% and make sodium phosphate：Amphoteric surfactant：The quality of EDTA is 2.4：1.2：There is preferable anti-plate when 0.03
Performance is tied, the effect for having mobility high.The centralized particle diameter degree of particle is high, is substantially differing between 8 mesh.
Embodiment 2
1000g carbon disulfide is added in there-necked flask, then, it is molten that the sodium permanganate that 100mL mass concentrations are 3% is added dropwise
Liquid after being added dropwise, continues agitator treating 50min, then stands 30min, is layered, and removes water phase, collects two after washing
Vulcanize carbon solution, for reacting in next step.Certainly, the mass concentration of above-mentioned sodium permanganate solution can also be 2%-5% with
Interior any percentage composition.
Then, 700g monomethylamine aqueous solutions then in another new clean there-necked flask are added in, wherein, monomethylamine aqueous solution
Mass concentration for 40% (being equivalent to 280g methylamine 9.0mol), it is molten that above-mentioned carbon disulfide is added dropwise at 20 DEG C -25 DEG C in control temperature
Liquid 380g (is equivalent to 5.0mol), after dripping, when continuation insulation reaction 2.5 is small, after reaction, carries out standing 30 minutes,
Layering, the carbon disulfide (can cover and use next group) for dividing sub-cloud extra collect the water containing N- methyl aminodithioformic acids
Solution is directly used in react in next step；Here carbon disulfide and the amount ratio of methylamine can be adjusted as needed, generally
The usage amount for making carbon disulfide is relatively excessive；
The formalin (being equivalent to 9.1mol formaldehyde) that 607g mass concentrations are 45% is added in another reactor,
4.0g potassium phosphates, 2.4g amphoteric surfactantes sulphonic acid betaine and 0.08g EDTA, then, control Wen Du ≤30 DEG C are opened
Begin that the aqueous solution obtained above containing N- methyl aminodithioformic acids is added dropwise, about dripped off when 5 is small or so, process is added dropwise
In can add in a small amount of antifoaming agent, be conducive to improve reaction efficiency, after dripping off, making pH value of reaction system, reaction terminates 7.5,
Then filter, filter cake is washed with clear water, obtains final product dazomet.Obtained dazomet is subjected to relevant performance survey
Examination, the results showed that, heap density is in 0.85g/cm3More than, content is more than 99.2%, and average grain diameter is 92 mesh, and the grain of particle
Footpath is distributed between -95 mesh of 86 mesh, and the distribution concentration degree of particle is good, yield 97.2%.And it is not tied during storage
Block phenomenon (6 months resting periods or more), product still have good mobility.As it can be seen that by using in advance in the present embodiment
Permanganate processing, and the addition of sodium phosphate is made to be the 1.5% of formaldehyde dosage and make potassium phosphate：Amphoteric surfactant：
The quality of EDTA is 4.0：2.4：When 0.08 there is preferable anti-compaction energy, there is the high effect of mobility, illustrate with compared with
Good synergistic effect.The centralized particle diameter degree of particle is high, is substantially differing between 9 mesh.
Embodiment 3
The pretreatment of carbon disulfide in the present embodiment is consistent with embodiment 1, and which is not described herein again.
700g monomethylamine aqueous solutions are added in clean there-necked flask, wherein, the mass concentration of monomethylamine aqueous solution is
The above-mentioned carbon disulfide solution 410g by pretreatment is added dropwise at 25 DEG C or so in 40% (being equivalent to 280g methylamines), control temperature,
After dripping, continue insulation reaction 2.5 it is small when, after reaction, carry out standing 30 minutes, layering, divide that sub-cloud is extra two
Nitric sulfid (can cover and use next group), collect the aqueous solution containing N- methyl aminodithioformic acids and be directly used in next step instead
It should；Here carbon disulfide and the amount ratio of methylamine can be adjusted as needed, generally make the usage amount phase of carbon disulfide
To excess；
The formalin (10mol formaldehyde) that 750g mass concentrations are 40%, 3.6g phosphoric acid are added in another reactor
Hydrogen potassium, 2.1g amphoteric surfactantes dodecyl ethyoxyl sulfobetaines and 0.04gEDTA, then, control Wen Du ≤
30 DEG C, start that the aqueous solution obtained above containing N- methyl aminodithioformic acids is added dropwise, about dripped off when 5 is small or so,
A small amount of antifoaming agent can be added in during dropwise addition, is conducive to improve reaction efficiency, after dripping off, makes pH value of reaction system 7.0, instead
It should terminate, then filter, filter cake is washed with clear water, obtains final product dazomet.Obtained dazomet is carried out relevant
Performance test, the results showed that, heap density is in 0.85g/cm3More than, for content more than 99.4%, average grain diameter is 93 mesh, and
The particle diameter distribution of grain is between -96 mesh of 88 mesh, and concentration degree is good, yield 97.8%.It is and existing without there is caking during storage
As (6 months resting periods or more), product still has good mobility.As it can be seen that by using Gao Meng in advance in the present embodiment
Hydrochlorate processing, and the addition of sodium phosphate is made to be the 1.2% of formaldehyde dosage and make potassium phosphate：Amphoteric surfactant：EDTA's
Quality is 3.6：2.1：There is preferable anti-compaction energy, the effect for having mobility high illustrates there is preferable association when 0.05
Same-action, the centralized particle diameter degree of particle is high, is substantially differing between 8 mesh.
Embodiment 4
The specific preparation method of this implementation is consistent with embodiment 3, differ only in obtain it is thio containing N- methyl two
Paraffin is added in carbamic aqueous solution, the addition for making the paraffin of addition is gross mass (N- methyl aminodithioformic acids
Aqueous solution weight) 1wt% or 2wt%.Finally obtain corresponding product dazomet.
Obtained dazomet is subjected to relevant performance test, the results showed that, heap density is in 0.85g/cm3More than, content exists
More than 99.2%, average grain diameter is 95 mesh, and the particle diameter distribution of particle, between -97 mesh of 90 mesh, concentration degree is good, and yield is
97.2%.And not occurring caking phenomenon (9 months resting periods or more) during storage, product still has flowing well
Property.As it can be seen that by adding a small amount of paraffin component, the anti-compaction energy of product can be more effectively improved, and still is able to make tool
There is the particle size distribution relatively concentrated.
Embodiment 5
The specific preparation method of this implementation is consistent with embodiment 3, differs only in, and amphoteric surfactant therein uses
The mixed surfactant of dodecyl ethyoxyl sulfobetaines and carboxylic acid glycine betaine, and make dodecyl ethyoxyl sulfo group sweet tea
The mass ratio of dish alkali and carboxylic acid glycine betaine is 1：0.2, other which is not described herein again.
Obtained dazomet is subjected to relevant performance test, the results showed that, heap density is in 0.85g/cm3More than, content exists
More than 99.1%, average grain diameter is 91 mesh, and the particle diameter distribution of particle, between -94 mesh of 86 mesh, concentration degree is good, and yield is
97.4%.And not occurring caking phenomenon (9 months resting periods or more) during storage, product still has flowing well
Property.
Embodiment 6
The specific preparation method of this implementation is consistent with embodiment 5, differs only in, and amphoteric surfactant therein uses
The mixed surfactant of dodecyl ethyoxyl sulfobetaines and carboxylic acid glycine betaine, and make dodecyl ethyoxyl sulfo group sweet tea
The mass ratio of dish alkali and carboxylic acid glycine betaine is 1：0.3, other which is not described herein again.
Obtained dazomet is subjected to relevant performance test, the results showed that, heap density is in 0.85g/cm3More than, content exists
More than 99.0%, average grain diameter is 89 mesh, and the particle diameter distribution of particle, between -92 mesh of 85 mesh, concentration degree is good, and yield is
97.0%.And not occurring caking phenomenon (9 months resting periods or more) during storage, product still has flowing well
Property.
Embodiment 7
The pretreatment of carbon disulfide in the present embodiment and step B's contains the water-soluble of N- methyl aminodithioformic acids
The preparation of liquid is consistent with embodiment 1, and which is not described herein again.
The formalin (being equivalent to 8.0mol formaldehyde) that 600g mass concentrations are 40% is added in another reactor,
2.4g phosphate, 1.2g amphoteric surfactantes dodecyl ethyoxyl sulfobetaines and 0.03gEDTA, can also make reaction
Baffle is equipped in device, baffle can be such as provided on the thermometer chuck in reactor, axial direction of the baffle along reactor
Direction so makes baffle have larger contact area, upon agitation, the product energy of precipitation in the reaction solution in reactor along stretching
It is enough that collision is generated baffle between, can so improve the effect of crystallization, so as to get dazomet particle with preferable uniformity
And size distribution concentration degree is high, then, control Wen Du ≤30 DEG C start to be added dropwise obtained above containing two thio ammonia of N- methyl
The aqueous solution of base formic acid about drips off when 5 is small or so, a small amount of antifoaming agent can be added in during dropwise addition, is conducive to improve anti-
Efficiency is answered, after dripping off, making pH value of reaction system, reaction terminates, and then filters, and filter cake is washed with clear water 7.5 or so,
Obtain final product dazomet.Obtained dazomet is subjected to relevant performance test, the results showed that, heap density is in 0.85g/cm3With
On, content is more than 99.1%, and average grain diameter is 92 mesh, and the particle diameter distribution of particle, between -94 mesh of 90 mesh, concentration degree is good,
Yield is 97.4%.And not occurring caking phenomenon (6 months resting periods or more) during storage, product still has good
Mobility.
Comparative example 1
In order to illustrate the advantage that the present invention pre-processes carbon disulfide using permanganate, this comparative example passes through direct
Specific implementation comparative descriptions are carried out using the carbon disulfide handled without permanganate.
700g monomethylamine aqueous solutions are added in clean there-necked flask, wherein, the mass concentration of monomethylamine aqueous solution is
35% (being equivalent to 245g methylamines (7.9mol)), control temperature exist<30 DEG C, it is added dropwise what is pre-processed without passing through sodium permanganate
Carbon disulfide solution 300g (3.9mol) after dripping, when continuation insulation reaction 2 is small, after reaction, carries out standing 30 points
Clock, layering, the carbon disulfide (can cover and use next group) for dividing sub-cloud extra are collected containing N- methyl aminodithioformic acids
Aqueous solution is directly used in react in next step；
The formalin (being equivalent to formaldehyde 8.0mol) that 600g mass concentrations are 40% is added in another reactor,
2.4g phosphate, 1.2g amphoteric surfactant carboxylic acid glycine betaines and 0.03gEDTA, then, control Wen Du ≤30 DEG C start
The aqueous solution obtained above containing N- methyl aminodithioformic acids is added dropwise, about drips off when 5 is small or so, after dripping off, makes
7.5 or so, reaction terminates pH value of reaction system, then filters, and filter cake is washed with clear water, obtains final product cotton
It is grand.Obtained dazomet is subjected to relevant performance test, the results showed that, heap density is in 0.7g/cm3More than, content is 95.8%
More than, average grain diameter is 95 mesh, and the particle diameter distribution of particle, between -102 mesh of 85 mesh, concentration degree is poor, yield 95.2%.And
The content of obtained product is relatively poor, and mobility is poor, under identical storage condition, can only store 2 months or so just to go out
Caking phenomenon is showed.It can be found that the content and yield of product all decrease, and the centralized particle diameter degree of particle is poor.
Comparative example 2
The specific preparation method of dazomet in this comparative example is consistent with embodiment 1, differs only in during step C
It does not add phosphate (sodium phosphate or potassium phosphate) to be embodied, other which is not described herein again.
Obtained dazomet is subjected to relevant performance test, the results showed that, heap density is in 0.7g/cm3More than, content exists
More than 95.6%, average grain diameter is 98 mesh, and the particle diameter distribution of particle has a very wide distribution between -110 mesh of 85 mesh, concentration degree
Difference, yield 95.0%.Mobility is poor, and under identical storage condition, can only storing 2 months or so, there have been lump now
As.It can be found that the content and yield of product all decrease, and the centralized particle diameter degree of particle is poor.
Pass through the results of property of above-mentioned comparative example 1 and comparative example 2, it may be said that it is bright the present invention using permanganate pretreatment and
Have between phosphate and preferably act synergistically, no matter when the two lacks any process, can not achieve and improve anti-plate
The effect of performance is tied, and the bulk density of product is relatively low, and can only achieve 0.7%g/cm3More than effect, content also compared with
It is low.And the distribution of grain size is wide, the range of 25 mesh of maximum difference between upper and lower grain size.
Comparative example 3
The specific preparation method of dazomet in this comparative example is consistent with embodiment 1, differs only in during step C
It does not add EDTA to be embodied, other which is not described herein again.
Obtained dazomet is subjected to relevant performance test, the results showed that, heap density is in 0.7g/cm3More than, content exists
More than 97.6%, average grain diameter is 110 mesh, and the particle diameter distribution of particle has a very wide distribution between -130 mesh of 90 mesh, concentration degree
Difference, yield 97.0%.Mobility is poor, and under identical storage condition, can only storing 3 months or so, there have been lump now
As.It can be found that the content and yield of product all decrease, and the centralized particle diameter degree of particle is poor.
Equally, the results of property of above-mentioned comparative example 1 and comparative example 3 is passed through, it may be said that the bright present invention is pre- using permanganate
It is also with what is preferably acted synergistically between processing and EDTA, no matter when the two lacks any process, can not achieve and carry
The effect of the hardened performance of highly resistance.And the bulk density of product is relatively low, and can only achieve 0.7%g/cm3More than effect, content
Relatively low, the distribution of grain size is wide, the range of 40 mesh of maximum difference between upper and lower grain size.
Comparative example 4
The specific preparation method of dazomet in this comparative example is consistent with embodiment 1, differs only in during step C
The phosphate (sodium phosphate or potassium phosphate) of addition is substituted for sodium sulphate, and the additive amount of sodium sulphate is embodied for 2.4g,
It is other which is not described herein again.
Obtained dazomet is subjected to relevant performance test, the results showed that, heap density is in 0.8g/cm3More than, content exists
More than 97.6%, average grain diameter is 120 mesh, and the particle diameter distribution of particle, between -130 mesh of 110 mesh, concentration degree is poor, yield
For 97.0%.Mobility is poor, under identical storage condition, can only store that there have been caking phenomenons in 3 months or so.It can be with
It was found that the content and yield of product all decrease, and the centralized particle diameter degree of particle is poor.Illustrate the present invention using phosphoric acid
Salt be can achieve the effect that it is unexpected, compared to other inorganic salts, in the concentration degree of particle diameter distribution and anti-hardened
Aspect of performance is respectively provided with extraordinary effect.Also the present invention is illustrated after by permanganate pretreatment, for adding in salt
Selection, which has, specifically to be required rather than any salt can be realized.
Comparative example 5
To properties of product and resist hardened and mobility influence in order to illustrate phosphatic addition in the present invention, this compares
Example is by making phosphatic addition be embodied below or above 1.0%~1.5% scope of the present invention.
The specific preparation method of dazomet in this comparative example is consistent with embodiment 1, differs only in during step C
The addition of the phosphate (sodium phosphate or potassium phosphate) of addition carries out for 0.5% (1.2g) or 2.0% (4.8g) of formaldehyde quality
Specific implementation, other which is not described herein again.
Obtained dazomet is subjected to relevant performance test, the results showed that, either relatively low or higher, obtained production
The heap density of product can only achieve in 0.75g/cm3More than, content is more than 96.6%, and average grain diameter is 122 mesh, and the grain of particle
Footpath is distributed between -135 mesh of 100 mesh, and concentration degree is poor, yield 97.4%.Mobility is poor, in identical storage condition
Under, it can only store that there have been caking phenomenons in 3 months or so.It can be found that the content and yield of product all decrease, and
The centralized particle diameter degree of grain is poor, and range intervals are excessive.
Specific embodiment described in the present invention is only to spirit explanation for example of the invention.Technology belonging to the present invention is led
The technical staff in domain can do various modifications or additions to described specific embodiment or replace in a similar way
Generation, but without departing from spirit of the invention or beyond the scope of the appended claims.
It is skilled to this field although having been made a detailed description to the present invention and being cited some specific embodiments
For technical staff, as long as it is obvious that can make various changes or correct without departing from the spirit and scope of the present invention.
Claims (7)
1. a kind of anti-hardened dazomet preparation method, which is characterized in that this method comprises the following steps：
A, permanganate water solution is added in carbon disulfide solution to be pre-processed, be layered, collect two sulphur by pretreatment
Change carbon solution；
B, reacted what step A was obtained by the carbon disulfide solution pre-processed with dense methylamine water solution, after reaction,
Layering removes oil phase, obtains the aqueous solution containing N- methyl aminodithioformic acids；The mass concentration of the dense methylamine water solution
≥30%；
C, in the presence of phosphate, amphoteric surfactant and EDTA, make containing the water-soluble of N- methyl aminodithioformic acids
Liquid is reacted with formaldehyde, obtains dazomet；The phosphatic addition is the 1.0%~1.5% of the quality of formaldehyde, the phosphoric acid
Salt：Amophoteric surface active：The mass ratio of EDTA is 1：0.5~0.6：0.01~0.02；The amphoteric surfactant is selected from carboxylic
One or more of sour glycine betaine, sulphonic acid betaine and dodecyl ethyoxyl sulfobetaines.
2. resist hardened dazomet preparation method according to claim 1, which is characterized in that dense methylamine is water-soluble described in step B
The mass concentration of liquid is 35wt%~40wt%.
3. resist hardened dazomet preparation method according to claim 1, which is characterized in that phosphate is selected from described in step C
One or more of potassium phosphate, sodium phosphate, dibastic sodium phosphate or potassium hydrogen phosphate.
4. according to the anti-hardened dazomet preparation method of claim 1 or 2 or 3, which is characterized in that step C is specially：
Phosphate, amphoteric surfactant and EDTA are added in reaction kettle, then adds formalin, controls reactant
Temperature≤30 DEG C of system, then the aqueous solution containing N- methyl aminodithioformic acids is added dropwise, antifoaming agent, drop are added in during being added dropwise
After adding, making the pH value of reaction system, after reaction, crystallization filters, obtains dazomet 7.0~7.5.
5. according to the anti-hardened dazomet preparation method of claim 1 or 2 or 3, which is characterized in that contain described in step B
Added with paraffin in the aqueous solution of N- methyl aminodithioformic acids, the addition of the paraffin for gross mass 1wt%~
2wt%。
6. according to the anti-hardened dazomet preparation method of claim 1 or 2 or 3, which is characterized in that Gao Meng described in step A
Hydrochlorate is selected from sodium permanganate or potassium permanganate.
7. resist hardened dazomet preparation method according to claim 1, which is characterized in that the amphoteric surfactant is carboxylic
The mixture of sour glycine betaine and dodecyl ethyoxyl sulfobetaines, and the dodecyl ethyoxyl sulfobetaines and carboxylic
The mass ratio of sour glycine betaine is 1：0.2~0.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710938723.XA CN107540635B (en) | 2017-09-30 | 2017-09-30 | A kind of anti-hardened dazomet preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710938723.XA CN107540635B (en) | 2017-09-30 | 2017-09-30 | A kind of anti-hardened dazomet preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107540635A CN107540635A (en) | 2018-01-05 |
| CN107540635B true CN107540635B (en) | 2018-05-22 |
Family
ID=60967496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710938723.XA Active CN107540635B (en) | 2017-09-30 | 2017-09-30 | A kind of anti-hardened dazomet preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107540635B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109997587B (en) * | 2019-03-22 | 2021-07-13 | 台州市农业科学研究院 | Replanting method for continuous cropping sweet cherry orchard in warm wetland area in south |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5495017A (en) * | 1991-12-21 | 1996-02-27 | Basf Aktiengesellschaft | Preparation of substantially dust-free tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione granules |
| CN102391165A (en) * | 2011-10-18 | 2012-03-28 | 利民化工股份有限公司 | Process for producing potassium N-methyldithiocarbamate |
| CN106831649A (en) * | 2016-12-27 | 2017-06-13 | 浙江海正化工股份有限公司 | A kind of dazomet preparation technology |
-
2017
- 2017-09-30 CN CN201710938723.XA patent/CN107540635B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5495017A (en) * | 1991-12-21 | 1996-02-27 | Basf Aktiengesellschaft | Preparation of substantially dust-free tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione granules |
| CN102391165A (en) * | 2011-10-18 | 2012-03-28 | 利民化工股份有限公司 | Process for producing potassium N-methyldithiocarbamate |
| CN106831649A (en) * | 2016-12-27 | 2017-06-13 | 浙江海正化工股份有限公司 | A kind of dazomet preparation technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107540635A (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102190521B (en) | Water-soluble fertilizer containing humic acid chelating multielement and preparation method thereof | |
| CN101058522B (en) | Leaf surface fertilizer for composite amino acid chelate complex | |
| CN1331823C (en) | Foliage fertilizer special for bean family forage grass | |
| CN1295195C (en) | Organic iron fertilizer | |
| Barčauskaitė et al. | Mechanochemically synthesized gypsum and gypsum drywall waste cocrystals with urea for enhanced environmental sustainability fertilizers | |
| CN107540635B (en) | A kind of anti-hardened dazomet preparation method | |
| CN108586100A (en) | A kind of foliar fertilizer and preparation method thereof | |
| CN102701824A (en) | Production method for macro-element water-soluble fertilizer | |
| CN107216190A (en) | A kind of nitre sulfenyl calcium and magnesium fertilizer production method of stabilization | |
| CN102602980A (en) | Industrial preparation method of alkali copper sulfate | |
| CN101368103A (en) | Soil conditioner for preventing and controlling azotate pollution of facilities vegetable and method of producing the same | |
| CN102060609A (en) | Liquid composite foliar fertilizer special for rape | |
| CN105777345A (en) | Production method of nanometer humic acid chelated zinc, manganese and iron composite micro fertilizer | |
| CN106831461B (en) | A kind of synthesis technology of four sodium of iminodisuccinic acid | |
| CN109438266B (en) | Environment-friendly iminodisuccinic acid chelated metal salt | |
| RU2407722C2 (en) | Method for production of highly concentrated solution of mineral fertiliser for treatment of plant leaves | |
| CN1765839A (en) | Organic zinc fertilizer | |
| WO1993021134A1 (en) | Combinations of active substances for preventing or regulating the nitrification of ammonium nitrogen in arable grounds and substrates | |
| CN107652094A (en) | The Water soluble fertilizer of a kind of balanced type containing humic acid and preparation method thereof | |
| RU2509724C1 (en) | Method of producing highly pure calcium carbonate and nitrogen-sulphate fertiliser during complex processing of phosphogypsum | |
| CN104609926B (en) | A kind of method that utilization phosphoric acid by wet process prepares high-quality polynary water soluble composite fertilizer | |
| CN106831176A (en) | A kind of antiacid alga fertilizer and its manufacture method | |
| CN108530226A (en) | A kind of highly acid composite fertilizer that phosphorus potassium utilization rate can be made to improve 3 to 5 times | |
| CN1206165C (en) | Preparation of chromium anhydride | |
| CN110655116A (en) | Preparation method of agricultural manganese sulfate solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 317016 Taizhou City, Zhejiang Province, Zhejiang province chemical raw material base near the sea area Patentee after: Zhejiang Dapeng Pharmaceutical Co., Ltd Address before: 317016 Taizhou City, Zhejiang Province, Zhejiang province chemical raw material base near the sea area Patentee before: TAIZHOU DAPENG PHARMACEUTICAL Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of Millon resistant to hardening Effective date of registration: 20211112 Granted publication date: 20180522 Pledgee: Industrial and Commercial Bank of China Limited Linhai Branch Pledgor: Zhejiang Dapeng Pharmaceutical Co.,Ltd. Registration number: Y2021330002244 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |