CN106699536A - Preparation method of anhydrous formaldehyde alcohol solution and device - Google Patents
Preparation method of anhydrous formaldehyde alcohol solution and device Download PDFInfo
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- CN106699536A CN106699536A CN201710021891.2A CN201710021891A CN106699536A CN 106699536 A CN106699536 A CN 106699536A CN 201710021891 A CN201710021891 A CN 201710021891A CN 106699536 A CN106699536 A CN 106699536A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
- C07C45/84—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by azeotropic distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/86—Use of additives, e.g. for stabilisation
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Abstract
The invention relates to a preparation method of an anhydrous formaldehyde alcohol solution and a device, and belongs to the technical field of chemical industry production. The invention particularly relates to an integrated device. The integrated reactor is particularly provided with a concentrated formaldehyde feeding opening, a polymerization catalyst feeding opening, an alcohol feeding opening, a depolymerization catalyst and polymerization inhibition stabilizer feeding opening, a vacuum opening and a gas phase pressure equalizing pipeline. Through one-step reaction in the integrated device, processes of formaldehyde aqueous solution dehydration, polymerization and depolymerization are achieved; meanwhile, through use of a catalyst and a stabilizer, the quality stability is improved; the prepared anhydrous formaldehyde alcohol solution provides an ideal anhydrous liquid formaldehyde source, and is especially applicable to organic synthesis reaction processes, in which anhydrous formaldehyde participates, during production of glyphosate, alachlor, acetochlor, butachlor, phorate and other products; the device provided by the invention and synthesizing devices of the former products are clustered nearby and are constructed in a matching manner, so that the benefits of the device provided by the invention can be maximized.
Description
Technical field
The present invention relates to the preparation method and device of a kind of anhydrous formaldehyde alcoholic solution, belong to chemical production technical field.Should
Anhydrous formaldehyde alcoholic solution is a kind of preferable nonaqueous liquid formaldehyde source, is that formalin and a kind of of paraformaldehyde replace well
Dai Pin.
Background technology
（One）Formaldehyde brief introduction
Formaldehyde（Molecular formula HCHO）It is a kind of gas flammable, colourless, excitatory.Soluble in water, alcohol, ketone and ether.
Formaldehyde has larger harm to human body.For a long time, low concentration Formaldehyde Exposed can cause headache, dizziness, it is furious itch, it is weak,
Drowsiness, uncomfortable in chest, asthma, sneeze, dermatitis, skin and mucous membrane irritation damage, sensory disturbance, immunity reduction, failure of memory, nerve
Allergic symptom or the illnesss such as weak, mental depression, respiratory dysfunction, hepatogenotoxicity lesion, and have carcinogenic, teratogenesis and cause base
Because of mutation effect.
Formaldehyde is a kind of important basic organic chemical raw material, be mainly used in synthetic plastic, synthetic resin, chemical fibre, dyestuff,
The industries such as coating, medicine, agricultural chemicals.It is industrial be often prepared as the water-soluble dope of formaldehyde, content of formaldehyde 37% or so, it 35~40%
Formalin is called and makees formalin.Formaldehyde is water-soluble to be susceptible to polymerisation, the polyformaldehyde precipitation of white is generated, in low temperature
Under the conditions of it is particularly evident, in general merchandise formaldehyde, all add 10%~15% methyl alcohol as polymerization inhibitor.
But due to low boiling point, property is active, exist that industrial goods water content is high, bin stability is poor, packing instructions are high, fortune
Defeated high cost, using disadvantages such as inconvenience, consider to be not easy to long-distance transportation from safety and economic angle and easily use, so
Typically all set up factories near the main consumption market in downstream, or be further prepared as the paraformaldehyde of solid-state.
（Two）Anhydrous formaldehyde application
Many organic synthesis with formaldehyde as raw material are to avoid water reaction, and the presence of water can cause side reaction so as to influence to receive
Rate, quality, or even cause the reaction cannot to carry out.In this case, it is desirable to which reaction system is anhydrous or micro water state, so
Formalin is not applied to.
But the separation of formaldehyde and water, concentration are a problems.Formaldehyde and water are a special systems for complexity, mainly
Formaldehyde and water have association in vapour, liquid two-phase, and with the difference of content of formaldehyde, the association ratio of formaldehyde and water is different,
Boiling point is also different, and general method is difficult to separate.
Industrially, paraformaldehyde is generally used to be substituted.Paraformaldehyde has wide as the substitute product of formaldehyde
Market, is described as preferable pure formaldehyde source.But during practical application in industry, paraformaldehyde there is also many shortcomings（Under
Text is described in detail）.
The preparation method and device of the anhydrous formaldehyde alcoholic solution that the present invention is provided, can solve or evade this of paraformaldehyde
A little shortcomings.
（Three）Paraformaldehyde brief introduction
Paraformaldehyde（Molecular formula HO- (CH2O) n-H, wherein n=8~100）, it is a kind of white flammable nothing for having a formaldehyde odor
Amorphous pellets or powder, are soluble in hot water, are slightly soluble in cold water, can be dissolved in diluted acid and diluted alkaline.The same formaldehyde of its harm to human body, separately
Also there is dust harzard outward.
Industrially, by formalin through evaporation and concentration, condensation polymerization, dehydrate prepared, content is generally 91-97%,
Chemical property and purposes are substantially similar to formaldehyde, are the fabulous substitutes of the industrial formol aqueous solution.It is solid product, is effectively contained
Amount is high, convenient transport, economy, and the metering proportion that feeds intake is accurate, water-soluble also preferable, it is convenient to which to prepare formaldehyde water-soluble for dissolving again
Liquid, also can carry out depolymerization and reaction with organic solvent, be described as preferable pure formaldehyde source.
Mainly there are the links such as concentration, drying by the process of formalin paraformaldehyde, wherein concentration link technique base
This is identical, and drying link prevailing technology has the drying of autoclave concentrate drying, vacuum rake type or Wiper blade type, metal belt to dry, spray
Mist method is dried, azeotropic distillation is dried etc..
（Four）Problem in the deficiency and application process of paraformaldehyde
In industrial processes, all there are shortcomings in paraformaldehyde in production process and downstream using two aspects of operation：
One is production process and is related to paraformaldehyde dust and steam, production scene operating environment during lower procedure feeds intake
Difference, harm and risk with formaldehyde gas injury and dust injury, is unfavorable for employee's occupational health, and with dust and formaldehyde
Steam（Objectively there is the situation for decomposing generation formaldehyde vapor in paraformaldehyde storage and transport process）Burning, blast hair security risk.
According to statistics, almost all of use drag conveyer conveys the manufacturer of paraformaldehyde, and the link all occurred dust and first
Aldehyde steam pyrophoricity accident.
Two is that paraformaldehyde is smashed, sieved, packaging and lower procedure feed intake process for intermittently operated, automaticity
Low, work efficiency is low, and operating environment is poor, and the operating time is long, and labour intensity is big.
Three is that the quality index stability such as the paraformaldehyde degree of polymerization and main content is poor.Paraformaldehyde belongs to high molecular polymer,
The quality index influence factor such as its degree of polymerization and main content is more, control requires high, therefore objective during actual industrial production deposits
In the unstable problem of quality such as unstable, poorly water-soluble of the degree of polymerization.In addition, paraformaldehyde still is occurring to gather during storage
Reaction is closed, the degree of polymerization constantly increases, and causes dissolubility to be deteriorated, client's user satisfaction declines.Domestic only Zhenjiang Li Changrong companies
Paraformaldehyde control of product quality etc. a small amount of enterprise is relatively stablized, and reaches first-class level.
Four is that paraformaldehyde packaging bag belongs to dangerous waste, is not easy to disposal.Paraformaldehyde is solid state, and industrial processes are adopted
Be packed in bag packaging,《National Hazard waste register》The packing material is clearly defined as hazardous waste, must be carried out according to hazardous waste
Management, disposal and utilization, to prevent and treat environmental pollution, environmental protection and health.
（Five）Green chemical industry, recycling economy and circulation industrial zone background
With highlighting for chemical industry problem of environmental pollution, green chemical industry, recycling economy and circulation industrial zone are increasingly pushed away
It is high.Recycling economy has particularly important war for the development of Chinese Enterprises, industry or even society and the protection of ecological environment
Omit meaning.The development of enterprise, industry is driven with the theory of recycling economy, investment can be not only pulled, be promoted economic stability to increase,
Industry restructuring can also be promoted, clustering, chain and industrial upgrading is promoted, the utilization of resources and comprehensive utilization of waste materials is improved
Efficiency, the organic unity that economizes on resources with environmental protection of realization.
The present invention promotes circulation and link between industry exactly based on this theory, is formaldehyde industry and glyphosate, first grass
The clustering of the organic synthesis industry such as the medicine such as amine, Acetochlor, butachlor, thimet, agricultural chemicals, chainization create meeting point.
The content of the invention
Present invention aim at the production method and device that provide a kind of anhydrous formaldehyde alcoholic solution, the anhydrous formaldehyde alcoholic solution
Specially formaldehyde participate in, a kind of preferable nonaqueous liquid formaldehyde source is provided to moisture content requirement organic synthesis higher,
It is a kind of good substitute of formalin and paraformaldehyde.
Technical scheme
In the inventive method, using one kind dry, polymerization and depolymerization integrated reactor, realize formalin dehydration, polymerization,
The step of depolymerization one is completed, a kind of alcoholic solution of the direct anhydrous formaldehyde of output, there is provided nonaqueous liquid formaldehyde source.
Integrated reacting implement body is provided with concentrated formaldehyde charging aperture, polymerization catalyst charging aperture, alcohol charging aperture, depolymerization catalyst
Agent and inhibition stabilizer charging aperture, vacuum port, gaseous pressure balance pipeline；Its outside setting chuck, by being passed through hot water or steaming
Vapour heating mode to dehydrate and depolymehzation process provide heat, controlling reaction temperature.
The function of above-mentioned drying, polymerization and depolymerization integrated reactor both can independently be taken on by 11-1, it is also possible to by anti-
Answer device 11-1, discharge duct 11-2（One section of closed discharge duct）And reactor 11-3 combinations are taken on.I.e.：The drying, polymerization and solution
Poly- integrated reactor, both can be the combination of single 11-1, or 11-1,11-2 and 11-3, with specific reference to operating mode
Selected with preference.
Solution process flow is as follows：
（1）Control in dilute formalin after main content >=35% of formaldehyde, to pump into formaldehyde enrichment facility and be concentrated, obtain formaldehyde
Main content is >=the 50% concentrated formaldehyde aqueous solution, it is then pumped into drying, polymerization and depolymerization integrated reactor, then adds polymerization and urges
Agent, vacuum dehydration drying is carried out under the conditions of vacuum 80-101kPa, 50-85 DEG C of temperature, while there is polymerisation, control
Reaction time 3-5 hours processed, obtain paraformaldehyde polymer；
（2）To dehydrate, be polymerized and depolymerization integrated reactor in paraformaldehyde polymer add alcohol, alcohol and paraformaldehyde
The mol ratio control of polymer（0.7~1.4）:1, while depolymerization catalyst is added, 35-55 DEG C of controlling reaction temperature, during control
Between more than 30-120 minutes, obtain the alcoholic solution of formaldehyde, then be added thereto to stabilizer, obtain anhydrous after being uniformly mixed
Formaldehyde alcoholic solution product, adopts toward anhydrous formaldehyde alcoholic solution storage tank.
（3）The tail gas of integrated reactor top removing, its main component is formaldehyde and water, obtains dilute through cooling and washing
Formaldehyde, returns to light formalin storage tank reuse.
（1）Use polymerization catalyst：In dehydration, dry and polymerization process, urged to polymerization is added in integrated reactor
Agent, to promote to be dehydrated and be polymerized, improves reaction speed and efficiency, reducing energy consumption, and avoid the formation of the polymer of high polymerization degree.
The polymerization catalyst has two classes, and a class is acidic catalyst, specially phosphoric acid, boric acid, four boron hydrogen sodium, formic acid, citric acid etc.
The combination of one or more in acidic materials；Another kind of is base catalyst, specially NaOH, organic bases material
（Triethylamine, diethylamine, aliphatic amine, diamine, tertiary amine, azanol, guanidine etc.）Deng the combination of one or more in alkaline matter.
Flexibly selected with specific reference to downstream customer requirement or technological requirement, add ratio 0.1-10%.
（2）Use depolymerization catalyst：After dehydration and polymerization process terminate, to addition alcohol in integrated reactor as molten
Agent, while adding depolymerization catalyst, to promote depolymerization, improves reaction speed and efficiency, it is ensured that the abundant depolymerization of polymer turns into first
Aldehyde, while reducing energy consumption.The depolymerization catalyst is specially triethylamine, diethylamine, aliphatic amine, diamine, tertiary amine, azanol, guanidine
The combination of one or more in the organic bases material such as class, adds ratio 0.1-10%.
（3）Use stabilizer：After depolymehzation process terminates, to stabilizer is added in integrated reactor, its effect has two：One
It is to avoid formaldehyde alcoholic solution that polymerisation generation white precipitate occurs at low temperatures；Two is to avoid reaction alcohol and formaldehyde in acid
Property under the conditions of there is the side reaction of the generation material such as acetal.
The stabilizer is specially triethylamine, aliphatic amine, cyclammonium, polyvinyl acetal, pentaerythrite, methenamine
The combination of one or more in, adds ratio 0.1-10%, and specific dosage is adjusted to 7- with by the pH value of formaldehyde alcoholic solution
14（Alkaline environment）It is standard；In addition, environment temperature is lower, the relative raising of ratio is added.
（4）Gaseous pressure balance pipe：Dehydrating, be polymerized and depolymerization integrated reactor and measuring tank 7,8 between set
Gaseous pressure balance pipe is equipped with, to balance measuring tank pressure, is easy to blanking.
Beneficial effect
1st, produce and do not produce dust using process, operating procedure is reduced, security risk reduction.
The anhydrous formaldehyde alcoholic solution of the direct output liquid of the method, is a kind of formaldehyde products of liquid, eliminates solid-state
Process that paraformaldehyde is smashed, sieved, packing and lower procedure solid feeds intake, serialization degree is improved, and operating procedure is few, can subtract
Light work intensity, save it is artificial, reduce production cost.
Above-mentioned 4 operating procedures（Smash, sieve, packaging and downstream feed intake）Production scene also no longer produce poly first
Aldehyde dust, it is to avoid the dust harzard of paraformaldehyde, improves production scene operating environment, reduces employee occupational health risk；Also
The danger of dust explosion during production and use is evaded.
Remarks：Former flow：The concentrated formaldehyde aqueous solution-drier-cooling（Obtain solid polyformaldehyde product）- it is transferred to material
Storehouse（Dust）- smash（Dust）- screening（Dust）-- packaging（Dust）- vehicles drive is to lower procedure or producer --- solid
Feed intake（Dust）--- intensification depolymerization（Obtain depolymerization liquid）-- organic synthesis；Existing flow：It is the concentrated formaldehyde aqueous solution-dry, poly-
Close and depolymerization integrated reactor（It is not required to cooling）-- the alcoholic solution of anhydrous formaldehyde（Depolymerization liquid）-- pumping, groove tank car are delivered to down
Trip operation or producer -- liquid feed -- organic synthesis.
, the method production formalin steady quality.
One is that the formalin water content that the method is produced is low, reaches " anhydrous " rank, can meet the organic conjunction for avoiding water
Into reaction requirement.
Two is that the formalin quality that the method is produced is easily controllable, and depolymerization is complete, only containing a small amount of dimerization or trimer,
Polymer without macromolecular, and water content is low（Reach " anhydrous " rank）.With respect to the solid-state paraformaldehyde degree of polymerization and main content etc.
The shortcoming of quality index stability difference and the practical challenges that Influence of production factor is more, quality control requirement is high, with advantage.Especially
Be thoroughly solve traditional vacuum rake dry etc. method production solid polyformaldehyde during drier discharge out it is unclean
Defect.
Three is the process and device, can be according to downstream client's manufacturing technique requirent, by regulating and controlling formaldehyde degree of dehydration
And in pilot process paraformaldehyde the degree of polymerization and moisture, the moisture of flexible modulation formaldehyde alcoholic solution, with respect to solid-state poly first
For the process of aldehyde product depolymerization, its water content is lowlyer controllable, preferably meets downstream processing requirements.
, product be liquid, conveying and convenient storage.Product can be used storage tank storage, can directly be pumped by utilidor
To lower procedure（Producer）Transported using or using groove tank car, for store solids paraformaldehyde, conveying is convenient, saves
Storage space, warehouse cost is low.
, packaging process low cost, and produced without packaging bag this hazardous waste.Packing material cost can be also saved, and is reduced
The yield of paraformaldehyde packaging bag this hazardous waste（Defined according to hazardous waste, paraformaldehyde packaging bag category is dangerous useless
Thing）.
, serialization degree it is high, and shorten the lower procedure reaction time.Improve downstream paraformaldehyde depolymehzation process serialization
Degree, shortens the depolymerization reaction time.Lower procedure liquid conveying and can feed intake, and be not required to other depolymerization, shorten lower operation anti-
Between seasonable.
, with industry clustering effects and supporting effect.For formaldehyde industry and glyphosate, alachlor, Acetochlor, butachlor,
The clustering of the organic synthesis industry such as the medicine such as thimet, agricultural chemicals, chainization create meeting point, promote circulation and chain between industry
Connect.It is particularly suited in the process of producing product such as glyphosate, alachlor, Acetochlor, butachlor, thimet being participated in anhydrous formaldehyde
Organic synthesis process, cluster, auxiliary construction maximizing are highlighted the synthesizer of the device and the said goods nearby
Benefit of the present invention.
Brief description of the drawings
Fig. 1 is anhydrous formaldehyde alcoholic solution process chart.
Wherein, 1. light formalin storage tank, 2. formaldehyde enrichment facility, the 3. water-soluble liquid storage tank of concentrated formaldehyde, 4. alcohol storage tank, 5.
Polymerization catalyst storage tank, 6. depolymerization catalyst storage tank, 7. polymerization catalyst measuring tank one, 8-1 depolymerization catalysts measuring tank one, 8-
2 depolymerization catalyst measuring tanks two, 9 gaseous pressure balance pipes one, 10-1 gaseous pressures balance pipe two, 10-2 gaseous pressure balance pipes
Three, 11-1 water dry, are polymerized and depolymerization integrated reactor, the closed discharge ducts of 11-2,11-3 depolymerizing reactors, 12 anhydrous formaldehydes
Alcoholic solution storage tank, 13 condensers, 14 water scrubbers.
Specific embodiment
Embodiment 1
Using piece alkali as polymerization catalyst, using methyl alcohol as solvent, using triethylamine as polymerization catalyst and stabilizer, nothing is produced
Water beetle aldehyde methanol solution, to glyphosate production, is described as follows：
1st, dehydrating drier polymerization procedure
By the light formalin pump of main content >=35% in light formalin storage tank 1 to formaldehyde enrichment facility 2, formaldehyde is obtained
Main content is 55% or so the concentrated formaldehyde aqueous solution, is then pumped into drying, is polymerized and depolymerization integrated reactor 11-1.
Then to adding piece alkali as polymerization catalyst in integrated reactor, dosage is concentrated formaldehyde aqueous solution gross weight
0.15%.Specially：In piece alkali input storage tank 5, piece alkali dosage is the 0.15% of concentrated formaldehyde aqueous solution gross weight, is diluted with water
Be 48% liquid caustic soda, in pumping into measuring tank 7, put into after metering dry, in polymerization and depolymerization integrated reactor 11-1.In vacuum
Vacuum dehydration drying is carried out under the conditions of degree 80-90kPa, 60-70 DEG C of temperature, while there is polymerisation, reaction time 3-5 is controlled
Hour, obtain paraformaldehyde polymer.
2nd, depolymehzation step
In depolymehzation process, using methyl alcohol as solvent, using triethylamine as depolymerization catalyst.Specially：Will be from solvent tank 4
（That is alcohol storage tank）In methyl alcohol quantitatively add into dehydrating, be polymerized and depolymerization integrated reactor 11-1（Or 11-3, it is specific poor
Do not see that the 5th trifle is described）It is interior, the mol ratio 1 of control methyl alcohol and formaldehyde:1.Depolymerization catalyst triethylamine is added simultaneously, adds ratio
Example rolls over the 1% of hundred weight for formaldehyde weight.50-55 DEG C of controlling reaction temperature, control time 50-60 minutes, obtains the methyl alcohol of formaldehyde
Solution.
3rd, stabilizer is added and formaldehyde alcoholic solution product preparing
With triethylamine used as stabilizers（Depolymerization catalyst selects triethylamine with stabilizer in this example）.After depolymehzation process terminates, will
Triethylamine in stabilizer storage tank 6-2 pumps into measuring tank 8（8-1 or 8-2）In, add the absolute methanol solution that ratio is formaldehyde total
The 0.1% of weight, puts into reactor 11-1 after metering（Or 11-3）In, it is uniformly mixed.The pH value of formaldehyde alcoholic solution is adjusted
To 8.0-9.0.
Then adopt afterwards toward storage tank 12, obtain anhydrous formaldehyde methanol solution product, its content of formaldehyde about 50%, methanol content is about
50% and trace water (less than 0.3%)（Water is combined because containing in paraformaldehyde, so existing in anhydrous formaldehyde methanol solution product
Micro-moisture, but can reach the production customer process requirement such as glyphosate）.
The anhydrous formaldehyde methanol solution can be delivered to lower operation by pipeline or tank car, for glyphosate production.Glyphosate
In production link, reactor is pumped into using pipeline, then successively the material such as addition glycine, dimethylphosphite, hydrochloric acid is carried out instead
Should, obtain glyphosate.
The technical process advantage is as follows：
Advantage 1：The anhydrous formaldehyde methanol solution can use pipeline, eliminate paraformaldehyde manufacturer smash, screening,
Packaging and downstream glyphosate synthesis producer solid polyformaldehyde feed intake process, can serialization charging, high degree of automation, work efficiency
Height, labour intensity is low, and operating environment improves.If formaldehyde alcoholic solution device is built with glyphosate synthesis matched with devices, can also be straight
Connect and use pipeline（Pumping is discharged to glyphosate synthesis kettle using potential difference）, further save logistics transportation link and phase
Answer cost.
Advantage 1：Because not using packaging bags, thus production and no longer produced using process paraformaldehyde packaging bag this
One dangerous waste, to prevent and treat environmental pollution.
Advantage 3：No longer there is dust injury health risk and dust without the factor such as paraformaldehyde dust and steam in overall process
And vapor flame and risk of explosion.
Advantage 4：The anhydrous formaldehyde methanol solution production process depolymerization fully, thoroughly, is given birth to compared to using solid polyformaldehyde
Produce for glyphosate, the main content's index of formaldehyde is more stablized.
Advantage 5：And the time that paraformaldehyde packs time and depolymerization reaction has been saved, under the conditions of device is not increased newly,
The production capacity of paraformaldehyde device and glyphosate device can be improved, doulbe-sides' victory is realized.
Embodiment 2
Using phosphoric acid as polymerization catalyst, using ethanol as solvent, using formic acid as polymerization catalyst, stablized with triethylamine
Agent, produces anhydrous formaldehyde ethanol solution, to Acetochlor production, is described as follows：
1st, dehydrating drier polymerization procedure
By the light formalin pump of main content 35-37% in light formalin storage tank 1 to formaldehyde enrichment facility 2, formaldehyde is obtained
Main content is 55% or so the concentrated formaldehyde aqueous solution, is then pumped into drying, is polymerized and depolymerization integrated reactor 11-1.
Then to adding phosphoric acid as polymerization catalyst in integrated reactor, dosage is concentrated formaldehyde aqueous solution gross weight
0.1%.Specially：In phosphoric acid input storage tank 5, phosphoric acid dosage is the 0.1% of concentrated formaldehyde aqueous solution gross weight, pumps into measuring tank
In 7, in input drying after metering, polymerization and depolymerization integrated reactor 11-1.In vacuum 80-90kPa, temperature 60-70
Vacuum dehydration drying is carried out under the conditions of DEG C, while there is polymerisation, reaction time 3-5 hour is controlled, paraformaldehyde is obtained and is gathered
Compound.
2nd, depolymehzation step
In depolymehzation process, using ethanol as solvent, using formic acid as depolymerization catalyst.Specially：Will be from solvent tank 4
（That is alcohol storage tank）In ethanol quantitatively add into dehydrating, be polymerized and depolymerization integrated reactor 11-1（Or 11-3, it is specific poor
Do not see that the 5th trifle is described）It is interior, the mol ratio 1.2 of control ethanol and formaldehyde:1.Depolymerization catalyst formic acid is added simultaneously, adds ratio
Example rolls over the 0.5% of hundred weight for formaldehyde.50-55 DEG C of controlling reaction temperature, control time 50-60 minutes, obtains anhydrous formaldehyde ethanol
Solution.
3rd, stabilizer is added and formaldehyde alcoholic solution product preparing
With triethylamine used as stabilizers（Depolymerization catalyst and stabilizer formic acid in this example）.After depolymehzation process terminates, will be steady
The triethylamine determined in agent storage tank 6-2 pumps into measuring tank 8（8-1 or 8-2）In, add the gross weight that ratio is anhydrous formaldehyde ethanol solution
0.1% or so of amount, puts into reactor 11-1 after metering（Or 11-3）In, it is uniformly mixed.By anhydrous formaldehyde ethanol solution
PH value is adjusted to 7.0-7.5.
Then adopt afterwards toward storage tank 12, obtain anhydrous formaldehyde ethanol solution product, its content of formaldehyde about 50%, ethanol content is about
50% and trace water（0.5%）（Water is combined because containing in paraformaldehyde, so existing in anhydrous formaldehyde ethanol solution product micro
Moisture, but can reach the production customer process requirement such as Acetochlor）.
The anhydrous formaldehyde ethanol solution can be delivered to lower operation by pipeline or tank car, for Acetochlor production.Acetochlor
In production link, reactor is pumped into using pipeline, be passed through hydrogen chloride gas, intermediate chloromethyl ether is obtained, then by chloromethane
Base ether and another raw material primary amide mix, and condensation reaction is carried out under the conditions of alkali lye, that is, Acetochlor is obtained.
The technical process advantage is as follows：
Advantage 1：The anhydrous formaldehyde ethanol solution can use pipeline, eliminate paraformaldehyde manufacturer smash, screening,
Packaging and downstream Acetochlor synthesis producer solid polyformaldehyde feed intake process, can serialization charging, high degree of automation, work efficiency
Height, labour intensity is low, and operating environment improves.If formaldehyde alcoholic solution device and Acetochlor synthesizer auxiliary construction, can also be straight
Connect and use pipeline（Pumping is discharged to Acetochlor reactor using potential difference）, further save logistics transportation link and phase
Answer cost.
Advantage 1：Because not using packaging bags, thus production and no longer produced using process paraformaldehyde packaging bag this
One dangerous waste, to prevent and treat environmental pollution.
Advantage 3：No longer there is dust injury health risk and dust without the factor such as paraformaldehyde dust and steam in overall process
And vapor flame and risk of explosion.
Advantage 4：The anhydrous formaldehyde alcoholic solution production process depolymerization fully, thoroughly, is produced compared to using solid polyformaldehyde
For Acetochlor, the main content's index of formaldehyde is more stablized.
Advantage 5：And the time that paraformaldehyde packs time and depolymerization reaction has been saved, under the conditions of device is not increased newly,
The production capacity of paraformaldehyde device and Acetochlor device can be improved, doulbe-sides' victory is realized.
Embodiment 3
Using phosphoric acid as polymerization catalyst, using n-butanol as solvent, using formic acid as polymerization catalyst, stablized with triethylamine
Agent, produces anhydrous formaldehyde butanol solution, to butachlor production, is described as follows：
1st, dehydrating drier polymerization procedure
By the light formalin pump of main content 35-37% in light formalin storage tank 1 to formaldehyde enrichment facility 2, formaldehyde is obtained
Main content is 55% or so the concentrated formaldehyde aqueous solution, is then pumped into drying, is polymerized and depolymerization integrated reactor 11-1.
Then to adding phosphoric acid as polymerization catalyst in integrated reactor, dosage is concentrated formaldehyde aqueous solution gross weight
0.1%.Specially：In phosphoric acid input storage tank 5, phosphoric acid dosage is the 0.1% of concentrated formaldehyde aqueous solution gross weight, pumps into measuring tank
In 7, in input drying after metering, polymerization and depolymerization integrated reactor 11-1.In vacuum 80-90kPa, temperature 60-70
Vacuum dehydration drying is carried out under the conditions of DEG C, while there is polymerisation, reaction time 3-5 hour is controlled, paraformaldehyde is obtained and is gathered
Compound.
2nd, depolymehzation step
In depolymehzation process, using n-butanol as solvent, using formic acid as depolymerization catalyst.Specially：Will be from solvent tank 4
（That is alcohol storage tank）In n-butanol quantitatively add into dehydrating, be polymerized and depolymerization integrated reactor 11-1（Or 11-3, specifically
Difference is shown in that the 5th trifle is described）It is interior, the mol ratio of control n-butanol and formaldehyde（1-1.2）:1.Depolymerization catalyst first is added simultaneously
Acid, adds ratio for formaldehyde rolls over the 0.5% of hundred weight.50-55 DEG C of controlling reaction temperature, control time 50-60 minutes, obtains nothing
Water beetle aldehyde butanol solution.
3rd, stabilizer is added and formaldehyde alcoholic solution product preparing
With triethylamine used as stabilizers（Depolymerization catalyst and stabilizer formic acid in this example）.After depolymehzation process terminates, will be steady
The triethylamine determined in agent storage tank 6-2 pumps into measuring tank 8（8-1 or 8-2）In, the ratio that adds is the total of anhydrous formaldehyde butanol solution
0.1% or so of weight, puts into reactor 11-1 after metering（Or 11-3）In, it is uniformly mixed.Anhydrous formaldehyde n-butanol is molten
The pH value of liquid is adjusted to 7.0-7.5.
Then adopt afterwards toward storage tank 12, obtain anhydrous formaldehyde butanol solution product, its content of formaldehyde about 50%, n-butanol contains
Amount about 50% and trace water（1%）（Water is combined because containing in paraformaldehyde, so existing in anhydrous formaldehyde butanol solution product
Micro-moisture, but can reach the production customer process requirement such as butachlor）.
The anhydrous formaldehyde butanol solution can be delivered to lower operation by pipeline or tank car, for butachlor production.Fourth grass
In amine production link, reactor is pumped into using pipeline, successively putting into two kinds of materials of 2,6 diethylanilines and chloracetyl chloride carries out alkene
Aminating reaction, acylation reaction and etherification reaction, are obtained butachlor.
Claims (9)
1. a kind of preparation method of anhydrous formaldehyde alcoholic solution, it is characterised in that comprise the following steps：
（1）Control in dilute formalin after main content >=35% of formaldehyde, to pump into formaldehyde enrichment facility and be concentrated, obtain formaldehyde
Main content is >=the 50% concentrated formaldehyde aqueous solution, it is then pumped into drying, polymerization and depolymerization integrated reactor, then adds polymerization and urges
Agent, vacuum dehydration drying is carried out under the conditions of vacuum 80-101kPa, 50-70 DEG C of temperature, while there is polymerisation, control
Reaction time 3-5 hours processed, obtain paraformaldehyde polymer；
（2）To dehydrate, be polymerized and depolymerization integrated reactor in paraformaldehyde polymer add alcohol, alcohol and paraformaldehyde
The mol ratio control of polymer（0.7~1.4）:1, while depolymerization catalyst is added, 35-55 DEG C of controlling reaction temperature, during control
Between 30-120 minutes, obtain the alcoholic solution of formaldehyde, then be added thereto to stabilizer, anhydrous formaldehyde is obtained after being uniformly mixed
Alcoholic solution product, adopts toward anhydrous formaldehyde alcoholic solution storage tank；
（3）The tail gas of integrated reactor top removing, its main component is formaldehyde and water, and dilute first is obtained through cooling and washing
Aldehyde, returns to light formalin storage tank reuse.
2. the preparation method of the anhydrous formaldehyde alcoholic solution described in claim 1, it is characterised in that the polymerization catalyst has two
Class, a class be acidic catalyst, specially the one kind in the acidic materials such as phosphoric acid, boric acid, four boron hydrogen sodium, formic acid, citric acid or
Several combinations；Another kind of is base catalyst, specially NaOH, triethylamine, diethylamine, aliphatic amine, diamine, uncle
The combination of one or more in amine, azanol, guanidine etc., adds ratio 0.1-10%.
3. the preparation method of the anhydrous formaldehyde alcoholic solution described in claim 1, it is characterised in that described depolymerization catalyst has two
Class a, class is acidic catalyst, the specially combination of one or more in the acidic materials such as phosphoric acid, boric acid, formic acid；It is another kind of
It is base catalyst, the specially combination of one or more in NaOH, triethylamine, diethylamine, azanol etc. adds ratio
0.1-10%。
4. the preparation method of the anhydrous formaldehyde alcoholic solution described in claim 1, it is characterised in that the stabilizer is triethylamine etc.
The combination of one or more in aliphatic amine, cyclammonium, polyvinyl acetal, pentaerythrite, methenamine etc., adds ratio
0.1-10%。
5. a kind of device for preparing anhydrous formaldehyde alcoholic solution, it is characterised in that light formalin storage tank（1）Concentrated with formaldehyde and filled
Put（2）Connection, formaldehyde enrichment facility（2）With the water-soluble liquid storage tank of concentrated formaldehyde（1）Connection, the water-soluble liquid storage tank of concentrated formaldehyde（1）With dehydration
Dry, be polymerized and depolymerization integrated reactor（11-1）Connection；
Polymerization catalyst storage tank（5）With polymerization catalyst measuring tank（7）Connection, polymerization catalyst measuring tank（7）With dehydrate,
Polymerization and depolymerization integrated reactor（11-1）Connection；
Alcohol storage tank（4）Through pipeline point two-way, all the way with dehydrate, be polymerized and depolymerization integrated reactor（11-1）Connection, one
Road and depolymerizing reactor（11-3）Connection；
Depolymerization catalyst storage tank（6-1）, stabilizer storage tank（6-2）Point two-way after converging through pipeline, all the way through depolymerization catalyst meter
Measuring tank one（8-1）It is connected to and dehydrates, is polymerized and depolymerization integrated reactor（11-1）；All the way through depolymerization catalyst measuring tank
Two（8-2）It is connected to depolymerizing reactor（11-3）；
Dehydrate, be polymerized and depolymerization integrated reactor（11-1）, depolymerizing reactor（11-3）Bottom connects after converging through pipeline
It is connected to anhydrous formaldehyde alcoholic solution storage tank（13）.
6. the device for preparing anhydrous formaldehyde alcoholic solution described in claim 5, it is characterised in that polymerization catalyst measuring tank（7）
Top is through gaseous pressure balance pipe one（9）With dehydrate, be polymerized and depolymerization integrated reactor（11-1）Connection.
7. the device for preparing anhydrous formaldehyde alcoholic solution described in claim 5, it is characterised in that depolymerization catalyst measuring tank one
（8-1）Top is through barometric pipe two（10-1）With dehydrate, be polymerized and depolymerization integrated reactor（11-1）Connection；Depolymerization
Catalyst gauge measuring tank two（8-2）Top is through barometric pipe three（10-2）With depolymerizing reactor（11-3）Connection.
8. the device for preparing anhydrous formaldehyde alcoholic solution described in claim 5, it is characterised in that dehydrate, be polymerized and depolymerization
Integrated reactor（11-1）, depolymerizing reactor（11-3）Top is connected to condenser after converging through pipeline（13）.
9. the device for preparing anhydrous formaldehyde alcoholic solution described in claim 5, it is characterised in that anhydrous formaldehyde alcoholic solution storage tank
（13）Light formalin storage tank is removed after water scrubber（1）.
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