CN101967114A - Continuous production method and continuous production device for synthesizing biruea - Google Patents
Continuous production method and continuous production device for synthesizing biruea Download PDFInfo
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- CN101967114A CN101967114A CN201010264112XA CN201010264112A CN101967114A CN 101967114 A CN101967114 A CN 101967114A CN 201010264112X A CN201010264112X A CN 201010264112XA CN 201010264112 A CN201010264112 A CN 201010264112A CN 101967114 A CN101967114 A CN 101967114A
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- 238000010924 continuous production Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 128
- 238000002425 crystallisation Methods 0.000 claims abstract description 69
- 230000008025 crystallization Effects 0.000 claims abstract description 65
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 36
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 31
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 30
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004202 carbamide Substances 0.000 claims abstract description 22
- 238000007599 discharging Methods 0.000 claims abstract description 17
- 239000000376 reactant Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 claims description 61
- 239000002245 particle Substances 0.000 claims description 50
- 239000002994 raw material Substances 0.000 claims description 40
- 230000003534 oscillatory effect Effects 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
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- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
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- 241000282326 Felis catus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 150000003863 ammonium salts Chemical class 0.000 description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/005—Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
- B01D9/0054—Use of anti-solvent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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Abstract
The invention discloses a continuous production method for synthesizing biruea, comprising the following steps of: (1) continuously adding hydrazine hydrate and a urea solution into the middle lower part of an oscillating flow tubular reaction crystallizer to react and generate biruea grains; (2) along with the processes of reaction and crystallization, gradually increasing the grain diameter of the biruea grains, settling the biruea grains at the bottom of the reaction crystallizer, continuously discharging the biruea grains settled at the bottom of the reaction crystallizer, separating solids and liquid and cleaning to obtain the biruea; and (3) continuously discharging mother liquid with unconverted reactants from the upper part of the reaction crystallizer and continuously discharging ammonia as a by-product from the top of the reaction crystallizer. The invention also discloses the oscillating flow tubular reaction crystallizer which is used for implementing the production method. The continuous production method is suitable for alkaline condensation technology, increases an average reaction rate, has high production capacity of unit reactor volume and can control the grain diameter of the biruea to separate subsequently and reduce purification cost.
Description
Technical field
The present invention relates to the synthetic field of chemical industry, relating in particular to a kind of is the serialization industrial process of the synthetic hydrazo-dicarbonamide of raw material with hydrazine hydrate and urea, belongs to environmentally friendly chemical production technical.
Background technology
Hydrazo-dicarbonamide (NH
2CONHNHCONH
2) be a kind of industrial chemical of synthetic, except that fire-proof additive and anti-molten additive, a large amount of as the raw material of producing ADC whipping agent (Cellmic C 121) as senior slipproofing agent, electric plastics.
One of hydrazo-dicarbonamide industrial process that extensively adopts is by hydrazine hydrate (N at present
2H
4H
2O) and urea (NH
2CONH
2) condensation reaction generate hydrazo-dicarbonamide, its chemical equation is:
N
2H
4·H
2O+2NH
2CONH
2＝NH
2CONHNHCONH
2+2NH
3+H
2O
Above-mentioned being reflected in the liquid phase carried out, thus when reaction proceed to hydrazo-dicarbonamide concentration greater than its saturation solubility after, hydrazo-dicarbonamide will be separated out from solution in crystallization, form the hydrazo-dicarbonamide particle.Therefore the industrialization building-up process of hydrazo-dicarbonamide is a reaction crystallization process, and the condensed phase in the reactor is the solid-liquid suspension system.
The pH value of liquid phase is different during according to reaction, the processing method of practical application can be divided into acid condensation process and alkaline condensation process again.
Acid condensation process adding mineral acid in the reaction feed liquid makes to be reflected under the sour environment and carries out, acid in ammonia that condensation reaction produces and the reaction solution further reaction generates ammonium salt, thereby the carrying out that helps condensation reaction, it is very fast relatively to make that the speed of condensation reaction is especially reacted the speed in later stage, and being issued to the required total reaction time of acceptable economically transformation efficiency in the periodical operation condition is about 10 hours.
Acid condensation process generates a large amount of ammonium salts in reaction process, contain a large amount of ammonia nitrogens in the liquid phase ejecta of reaction process, chemical oxygen demand (COD) (COD) is very high, causes the severe contamination to environment to threaten thus, causes the immense pressure and the high cost of subsequent wastewater treatment operation.
In view of acid condensation process in the above-mentioned shortcoming aspect the Environmental costs, the alkaline condensation process comparatively friendly to environment becomes the focus technology that industry is implemented sustainable development strategies.
The order of alkalescence condensation process is reflected under the weakly alkaline environment to be carried out, and the ammonia that condensation reaction produces is resolved the disengaging reaction solution and discharged with the gas phase form.Condensation reaction rate is slower under the alkaline environment, especially react the later stage, after concentration of reactants reduces, speed of reaction obviously eases up especially, therefore required total reaction time is very long under the periodical operation condition, usually need more than 1.5 times of acid condensation process, and still be difficult to reach gratifying per pass conversion.
The per pass conversion that a solution reaction later stage speed technique means slow, that per pass conversion is low is a controlling reactor on the chemical engineering science is a lower level, reaction process is carried out under the reactant concn conditions of higher all the time, thereby obtain higher production intensity, promptly in unit time and unit reactor volume, obtain higher reaction yield.Because per pass conversion is lower, in reactor discharge material, contain more unreacting material component, therefore these components need be separated back Returning reactor feed end recycle with reaction product, to obtain the reasonable raw material utilization ratio.Best production intensity will be by the one way space-time yield cost of reactor and the overall equilbrium decision between product separation and the unreacted material round-robin cost.
The reaction technology of above-mentioned band recycle stream both can be realized with andnon-continuous operation manner, also can realize with the operate continuously mode.
When adopting the operate continuously mode, reactor used residence time distribution (RTD) characteristic will be a key factor of the best production intensity height of determination device.Theoretical analysis shows, increase the chemical reaction of accelerating with reactant concn for speed of reaction, RTD has under the highest reactant concn that the reactor of piston flow characteristic can reach reaction process all the time in theory and carries out, thereby be higher than the reaction of zero level for reaction order, average response speed in this class reactor is the fastest, can obtain the highest best production intensity; The reactor that RTD has the continuous stir reactor characteristic then carries out under minimum reactant concn all the time because of reaction process, thereby is higher than the reaction of zero level for reaction order, and average response speed is the slowest, and the best production intensity that can access is minimum.
The RTD characteristic of the various real reaction devices of industrial application is between above-mentioned two kinds of limiting cases, therefore according to the characteristics of related chemical reaction, adopt and reactor types reasonable in design, make reactor RTD characteristic to helping improving best production intensity direction convergence as far as possible, just can form various processing method.
With hydrazine hydrate and urea be the chemical reaction of the synthetic hydrazo-dicarbonamide of raw material for the reaction order number average of two kinds of reaction masses greater than zero, therefore adopt the RTD characteristic more to help improving the production intensity of reactor near the type of reactor of piston flow.
Because chemical reaction and crystallisation process take place simultaneously in hydrazo-dicarbonamide is synthetic, so the carrying out that temperature in the reactor and concentration distribution not only will consider to help chemical reaction also need help crystallization formation and process of growth.From the angle of chemical reaction, temperature of reaction height then reaction rate constant is big, and speed of reaction is fast, helps improving per pass conversion.And from the angle of crystallisation process, temperature is different for the influence of different crystallisation stages.When the number density of crystallite in the solution and nucleus is hanged down, if the solution degree of supersaturation is too big, hydrazo-dicarbonamide is separated out too fast, then can generate a large amount of new nucleus fast, and make the growth deficiency of existing crystallite and nucleus, cause the median size of final crystallized product too small, be unfavorable for obtaining the solid-liquid lock out operation of hydrazo-dicarbonamide product.Therefore this stage should be with higher temperature operation, and the crystallization control precipitation rate makes the growth of existing crystallite and nucleus in the solution and ratio that new nucleus generates suitable.After the number density of crystallite in the solution and nucleus acquires a certain degree, then can strengthen degree of supersaturation, increase the crystallization impellent, accelerate the crystallization precipitation rate, make rapid grain growth, form bigger median size, both helped the solid-liquid lock out operation, help improving the unit volume productive rate of crystallizer again.Therefore this stage should be with lower temperature operation.
The reaction crystalizer of excellent property should be able to form different warm areas in inside, reaction and crystalline different steps are carried out in favourable warm area more, to obtain optimization effect.
At the hydrazo-dicarbonamide production field, no matter be to adopt acid condensation process or alkaline condensation process, present industrial installation uses stirring tank to be the principal reaction device mostly.When carrying out operate continuously with stirring tank, its RTD characteristic tends is bordering on continuous stir reactor, is disadvantageous to improving best production intensity therefore.At this shortcoming of stirring tank, generally one of method of Cai Yonging is to adopt the placed in-line mode of many stills to constitute combined reactor to improve the RTD characteristic.According to theoretical analysis, the RTD characteristic that infinite a plurality of stirring tank series connection are obtained can be approached piston flow, but this is impossible realize in practice.Even if the series connection of limited a plurality of stirring tanks, because the mass transport cost increases with the increase of still number between device manufacturing cost and still, the actual still number that can adopt also only limits to units, its RTD characteristic and piston flow have more greatly and depart from, and the best production intensity that therefore actual many stills cascade reaction device is reached still has gap greatly with the best production intensity that plug flow reactor can reach.
Adopt the bigger tubular reactor of length-to-diameter ratio can provide usually than stirring tank more near the RTD characteristic of piston flow.Therefore to many continuous flow procedures, tubular reactor is the option more excellent than the still of manying tandem arrangement.But for the hydrazo-dicarbonamide building-up reactions, especially alkaline condensation process, then there is significant disadvantages in common tubular reactor.Because the speed of alkaline condensation reaction is slower, needs the residence time of reaction mass in reactor longer.If fluidised form was to the influence of heat and mass speed in we considered to manage, wishing to flow is in the turbulent flow attitude, then will cause the length of reactive crystallization pipe very long.Reactive crystallization pipe with internal diameter 200mm is an example, as requires reynolds number Re to reach 1000, is that 0.5mPas and density are 900kg/m for viscosity
3Fluid, velocity in pipes need reach 0.0278m/s, if mean residence time needs 1 hour, then the reactive crystallization length of tube need reach 100m.For the reactive crystallization pipe of length like this, then need to be made into the geometry that comes and goes baffling, such structure product---gaseous ammonia and solid hydrazo-dicarbonamide particle motion and discharging problem in reactor that can induce reaction makes reactor be difficult to the steady and continuous operation.If adopt tubulation structure decrease reactive crystallization length of tube, then increase because of cross section of fluid channel is long-pending, will cause the flow velocity in the reactive crystallization pipe slow, very be unfavorable for the heat and mass transfer process in the reactor, and cause the accumulation problem of hydrazo-dicarbonamide particle in pipe.
Oscillatory flow tubular reactor is a kind of faster novel reactor of development in recent years, compares with stirring tank, and its RTD characteristic more levels off to piston flow, can reach the placed in-line level of dozens of stirring tank.Because the turbulence intensity of its interior flow field is determined by the oscillation intensity that is superimposed upon the oscillating flow on the average flow, also can produce strong turbulence even mean flow rate is very slow, and the heat and mass effect is significantly strengthened.Utilize the advantage of oscillatory flow tubular reactor to be designed to the oscillatory flow tubular type reaction crystalizer of positioned vertical, if liquid material adds the top discharge from the bottom of reaction crystalizer, liquid will form inverse motion with solid particles suspended, then in average flow that makes progress and oscillating flow field, periodically produce, under the combined action of the swirl flow that moves and bury in oblivion, can produce the selectivity suspension effect to the solids of different-grain diameter and proportion, make the suspension density of particle in reactor be exponential distribution from top to bottom according to the size of particle diameter and proportion, minimum particle is enriched in reaction crystalizer top, and the particle that particle diameter acquires a certain degree then is enriched in the reaction crystalizer bottom.
The ultimate principle of Oscillatory Flow Reactor and constructional feature can be further referring to following documents:
Wu Jia, Li Xiaoqing, Hu Xiaoping, woods sunrise. flow pattern research (I) PIV and the RTD experimental study of tubular type Oscillatory Flow Reactor. chemical reaction engineering and technology, 2005 (5);
Wu Jia, woods sunrise, Hu Xiaoping, Li Xiaoqing. flow model and simulation under flow pattern research (II) high oscillation intensity of tubular type Oscillatory Flow Reactor. chemical reaction engineering and technology, 2006 (5);
Li Wei, Hu Xiaoping, Wu Jia. the CFD research in conical ring baffle plate Oscillatory Flow Reactor flow field. chemical reaction engineering and technology, 2007 (6);
And Chinese patent open source literature CN 100318191C, CN 1295210C, CN101230022A, CN 101219973A, CN 1986524A, CN 1381442A, CN 1251350A etc.
These characteristics of oscillatory flow tubular type reaction crystalizer extremely are of value in the operate continuously mode carries out the hydrazo-dicarbonamide condensation reaction, and the room for promotion of technical progress is provided for the best production intensity that improves alkaline condensation process serialization production.
Summary of the invention
The invention provides a kind of method that is adapted at continuous production hydrazo-dicarbonamide under the alkaline condensation process condition,, further also reduce wastewater discharge and intractability to shorten the reaction times, to improve throughput.
A kind of continuous production method of continuous production hydrazo-dicarbonamide, step is as follows:
(1) hydrazine hydrate and urea soln are positioned at the feed(raw material)inlet of (middle part on the lower side), pipe reaction crystallizer middle and lower part continuous the adding, hydrazine hydrate and urea react in the pipe reaction crystallizer and crystallization generates the hydrazo-dicarbonamide particle;
(2) along with the carrying out that the hydrazo-dicarbonamide grain diameter increases gradually and, the hydrazo-dicarbonamide particle that is settled down to bottom the reaction crystalizer is discharged continuously of reaction and crystallisation process, obtain the hydrazo-dicarbonamide product through solid-liquid separation and washing again to the sedimentation of the bottom of reaction crystalizer;
(3) mother liquor that will contain unconverted reactant is discharged continuously from the top of reaction crystalizer; Byproduct of reaction ammonia is discharged continuously from the reaction crystalizer top.
By control material feeding amount, can control the residence time (0.5～3h) of reaction mass in reaction crystalizer, allow the per pass conversion of reaction component maintain moderate, reaction process is carried out under the higher faster reactant concn condition of speed of reaction, make reaction crystalizer have higher unit volume productive rate.And the liquid phase part from the material that discharge at reaction crystalizer bottom, top and top also contains more unreacted component, returns the recycle of preparation of raw material operation after treatment, to obtain rational total conversion rate.
The weight percent of the reaction crystalizer feed stream that the present invention is suitable for consists of hydrazine hydrate 4～40%, urea 10～60%, and more preferably hydrazine hydrate 15～30%, urea 30～60%.
For will be not the raw material recycled of complete reaction, as preferably:
The liquid phase material that solid-liquid separation described in the step (2) and washing produce returns the recycle of preparation of raw material operation, and the hydrazo-dicarbonamide particle that is settled down to the reaction crystalizer bottom is discharged continuously with slurry form, and the solid content of discharging slurry is 5%～70%.
The mother liquor that contains unconverted reactant described in the step (3) returns the recycle of preparation of raw material operation after discharging continuously from the top of reaction crystalizer, and the mother liquor that contains unconverted reactant can reuse after dehydration procedure is sloughed part moisture.
Hydrazine hydrate in the byproduct of reaction ammonia described in the step (3) is separated and is returned the recycle of preparation of raw material operation.
Can further improve the total recovery of reaction like this, and accomplish serialization production.
Continuous production method of the present invention adopts a kind of oscillatory flow tubular type reaction crystalizer of special construction, and this reaction crystalizer is made up of reactive crystallization pipe, material inlet, solid phase discharging mechanism, gas-liquid-solid separator, and is connected with the oscillatory flow producer.
The reactive crystallization pipe is vertically installed, and tube wall is made into bellows-shaped or turbulent baffle is set to form the eddy-currents field structure in straight tube, strengthens momentum, heat and mass transfer process.The aqueous solution of reactant feed hydrazine hydrate and urea adds reactive crystallization pipe inside from the material inlet of reactive crystallization pipe middle and lower part, and condensation reaction takes place, and generates product hydrazo-dicarbonamide and ammonia.
The solubleness of product hydrazo-dicarbonamide in water is very little in the inventive method, oversaturated hydrazo-dicarbonamide will be separated out the formation solid crystal from solution, exist in solution under the situation of a great deal of small hydrazo-dicarbonamide suspended particles, crystallization will preferentially be separated out at microparticle surfaces, and mean particle dia is increased.Under the additive effect of oscillating flow field and average flow field, (particle diameter＜0.01mm) major part will be suspended in reaction crystalizer top to the minor diameter particulate, (0.01mm＜particle diameter＜0.1mm) major part is suspended in the reaction crystalizer middle part to the intermediate diameters particulate, and particle diameter increases along with the increase of the residence time.When the diameter of hydrazo-dicarbonamide particle increases to a certain degree (behind the particle diameter＞0.1mm), the suspension effect in flow field has been not enough to offset the effect of gravity, the major diameter particle will be deposited to the bottom of reaction crystalizer gradually, discharge reaction crystalizer via solid phase discharging mechanism 3 with slurry form.
The slurry material of discharging reaction crystalizer at the bottom of the tower enters solid-liquid separation circuit 8 (can adopt whizzer or filter) and further separates wherein liquid, and isolated solid materials water is washed to obtain not contain the hydrazo-dicarbonamide product of hydrazine hydrate.
Flow velocity by regulating average flow (0.001～0.1m/s) and the amplitude of oscillating flow field (3～200mm) and frequency (0.1～10Hz), the hydrazo-dicarbonamide particle that can control effectively has bigger particle diameter, and (median size=0.1～0.5mm) helps solid-liquid separation and washing operation.Hydrazo-dicarbonamide particle after the washing can be sent to and carry out drying treatment, and isolated liquid and washing lotion are sent 9 recycles of preparation of raw material operation back to.
Another product ammonia has certain solubleness in water, oversaturated ammonia will be separated out the formation bubble from solution, the gas-liquid-solid separator that upwards shifts to reactor top along the reactive crystallization pipe separates with suspension, discharges reaction crystalizer via top gas phase discharge port again.The gaseous phase materials of discharging reclaims water and the micro-hydrazine hydrate of carrying secretly through ammonia separation circuit 7, delivers to follow-up operation then and further is processed into valuable ammonolysis product.
The aqueous solution of urea and hydrazine hydrate enters the average flow that forms behind the reactive crystallization pipe from bottom to top, and produces oscillating flow field under the excitation of clapp oscillator.Average flow becomes the adverse current state with the subsiding movement of hydrazo-dicarbonamide particle, thus the particle size growth of the hydrazo-dicarbonamide particle that helps suspending.The aqueous solution that contains intact urea of unreacted and hydrazine hydrate enters in the gas-liquid-solid separator on reactor top and gaseous ammonia and most of suspension hydrazo-dicarbonamide separate particles, carries the hydrazo-dicarbonamide particle of section diameter minimum then secretly and discharges reactor from the mother liquor discharge port.The mother liquor of discharging is delivered to the liquid mixing of dehydration procedure and solid-liquid separation circuit and is removed part moisture content, to offset the moisture content that the hydrazine hydrate stock liquid brings into, the moisture content that condensation reaction generates, the washing moisture content that the solid-liquid separation circuit is introduced, keep the water balance of system.Concentrated solution after the dehydration is delivered to the recycle of preparation of raw material operation.
The reactive crystallization pipe is provided with the segmentation heat exchange jacket, enter the heat medium temperature of each section chuck by adjusting, under can in the reactive crystallization pipe, forming low high axial temperature distribute (20～150 ℃), help forming the hydrazo-dicarbonamide crystal grain of greater particle size, obtain higher hydrazine hydrate per pass conversion on reactive crystallization pipe top in reactive crystallization pipe bottom.
Outside at gas-liquid-solid separator also is provided with heat exchange jacket, the heat medium temperature that adjusting enters this chuck makes gas-liquid-solid separator operate (100～150 ℃) under comparatively high temps, reduce the saturation solubility of ammonia in liquid material on the one hand, help separating out of by product ammonia; Reduce the density and the viscosity of liquid material on the other hand, help the sedimentation of hydrazo-dicarbonamide particle, reduce the suspended particles amount of carrying secretly of liquid discharging.
Continuous production method of the present invention, be characterized in the aqueous solution of hydrazine hydrate and urea is added oscillatory flow tubular type reaction crystalizer middle and lower part continuously, in the oscillating flow field of certain amplitude and frequency, carry out condensation reaction, generate target product hydrazo-dicarbonamide and water byproduct, ammonia.Compare with stirring tank, its RTD characteristic more levels off to piston flow, can reach the placed in-line level of dozens of stirring tank.Because the turbulence intensity of its interior flow field is determined by the oscillation intensity that is superimposed upon the oscillating flow on the average flow, also can produce strong turbulence even mean flow rate is very slow, and the heat and mass effect is significantly strengthened.Simultaneously because the effect of the whirlpool that periodically produces in its internal oscillator flow field, moves and bury in oblivion, can produce the selectivity suspension effect to the solids of different-grain diameter and proportion, make the suspension density of particle in reaction crystalizer be exponential distribution from top to bottom according to the size of particle diameter and proportion, the particle that particle diameter acquires a certain degree then can be enriched in reactor bottom.These characteristics of oscillatory flow tubular type reaction crystalizer extremely are of value in the operate continuously mode carries out the hydrazo-dicarbonamide condensation reaction, and the room for promotion of technical progress is provided for the best production intensity that improves alkaline condensation process serialization production.
In order to implement continuous production method of the present invention, the present invention also provides a kind of oscillatory flow tubular type reaction crystalizer, comprises the reactive crystallization pipe.Described reactive crystallization pipe is vertically arranged, reactive crystallization pipe top is provided with gas-solid-liquid/gas separator, gas-solid-liquid/gas separator side has the liquid phase discharge port that is used to discharge the mother liquor that contains unconverted reactant, the top of gas-solid-liquid/gas separator is provided with the gas phase discharge port that is used to get rid of ammonia, reactive crystallization pipe middle and lower part is provided with the feed(raw material)inlet, reactive crystallization pipe bottom is provided with and is used to discharge hydrazo-dicarbonamide particulate products export, and the position of reactive crystallization pipe between feed(raw material)inlet and products export is provided with the oscillatory flow producer.
For the oscillatory flow tubular type reaction crystalizer that promotes the homodisperse of material in the reactor, preferably adopt to have the conical ring baffle plate in the reactive crystallization pipe.
Oscillatory flow producer and conical ring baffle plate all can adopt prior art.
In order to guarantee the necessary reaction zone length in top, feed(raw material)inlet, and deposition hydrazo-dicarbonamide particulate space is collected in the below, feed(raw material)inlet, as preferably, the reactive crystallization length of tube of feed(raw material)inlet below be the top, feed(raw material)inlet the reactive crystallization length of tube 10%～60%, further preferred 20%～40%.
As preferably, described gas-solid-be provided with traverse baffle or filter screen in the liquid/gas separator, can reach better gas-solid-liquid separating effect.
In oscillatory flow tubular reactor, utilize the selectivity suspension effect of its oscillating flow field to solia particle, the less hydrazo-dicarbonamide particle of particle diameter is suspended in the reactor middle part, further the hydrazo-dicarbonamide that generates of reaction is separated out from solution and is attached to its surface and makes particle continue to grow up, the particle that particle diameter reaches certain value then is deposited to reactor bottom, discharge reactor by discharging mechanism with the slurry form, carry out further solid-liquid separation and washing, obtain possessing the hydrazo-dicarbonamide particle of certain particle size.The hydrazo-dicarbonamide particle grain size can be regulated and control in 0.01～0.5mm scope by the operating parameters that changes Oscillatory Flow Reactor.
The present invention has made full use of residence time of material narrowly distributing in the Oscillatory Flow Reactor, solids has been possessed the characteristics of selectivity suspension effect, thereby the throughput with unit reactor volume is big, and the particle diameter of may command product hydrazo-dicarbonamide is so that the advantage that follow-up separation and purification cost reduce.
Description of drawings
Fig. 1 is the apparatus structure synoptic diagram of the embodiment of the invention 1 continuous production hydrazo-dicarbonamide.
Fig. 2 is the apparatus structure synoptic diagram of the embodiment of the invention 2 continuous production hydrazo-dicarbonamides.
Embodiment
Oscillatory flow tubular type reaction crystalizer of the present invention, comprise reactive crystallization pipe 1, reactive crystallization pipe 1 is vertically arranged, there is heat exchanger 12 outside, reactive crystallization pipe 1 top is provided with gas-solid-liquid/gas separator 4, gas-solid-liquid/gas separator 4 sides have the liquid phase discharge port 6 that is used to discharge the mother liquor that contains unconverted reactant, the top of gas-solid-liquid/gas separator 4 is provided with the gas phase discharge port 5 that is used to get rid of ammonia, reactive crystallization pipe 1 middle and lower part is provided with feed(raw material)inlet 2, reactive crystallization pipe 1 bottom is provided with and is used to discharge hydrazo-dicarbonamide particulate products export, and the position of reactive crystallization pipe 1 between feed(raw material)inlet 2 and products export is provided with concussion producer 10.
As supporting, be provided with the preparation of raw material still 9 that is used for mixing raw material;
Be provided with the hydrazine hydrate withdrawer 7 of the hydrazine hydrate that is used for separating by-products ammonia;
Be provided with dehydration procedure, adopt still formula vaporizer 11, normal pressure operation down;
The products export place of reactive crystallization pipe 1 bottom is provided with discharger 3, and discharger 3 exits are provided with and are used for equipment for separating liquid from solid 8.
Embodiment 1
Oscillatory flow tubular type reaction crystalizer as shown in Figure 1, reactive crystallization bore 150mm, height 12000mm, turbulent baffle adopts the conical ring baffle plate of percentage of open area 25%; The reactive crystallization pipe is provided with four sections heat exchange jackets outward, regulates each section heating agent temperature in, makes the temperature distribution in the reactive crystallization pipe be respectively 50,90,105,110 ℃ from bottom to top; Reactive crystallization pipe bottom configuration plunger hydraulic barrier film oscillatory flow producer, oscillation frequency is 1～3Hz, amplitude 5～50mm; Gas-liquid-solid separator internal diameter 600mm, the top is provided with wire mesh demister, the outer setting heat exchange jacket, it is 110～120 ℃ that adjusting heating agent inlet temperature makes the liquidus temperature in the separator; The solid phase discharging mechanism adopts spiral discharger; The reaction crystalizer working pressure is 0.3MPa.
Reactive crystallization pipe 1 length of 2 belows, feed(raw material)inlet be 2 tops, feed(raw material)inlet reactive crystallization pipe 1 length 30%.
The employing of preparation of raw material operation has the continuous stirred tank realization recycle stock of heating jacket and mixing of raw material hydrazine hydrate and urea, and prepared materials percentage ratio meter by weight contains hydrazine hydrate 25%, urea 50%, and surplus is a water; Add reactor down at 100 ℃, feeding rate is 320kg/h.
The ammonia separation circuit adopts stripping tower, and column internals adopts flow through type multi-step angular tower plate, and atmospheric operation is established kettle-type reboiler at the bottom of the tower, and rising steam is than 0.1, and the ammonia steam of cat head is sent to making ammoniacal liquor, and still liquid hydrazine hydrate is sent the recycle of preparation of raw material still back to.
The solid-liquid separation circuit adopts band filter, filter cake clear water countercurrent washing three times.Filtrate and washings are delivered to the recycle of preparation of raw material still, and the filter cake after the washing is the hydrazo-dicarbonamide product, can get the hydrazo-dicarbonamide particle 62kg/h of the about 0.1mm of median size after the drying.
As shown in Figure 2, the reactive crystallization pipe adopts ripple inwall jacket pipe, ripple inwall maximum inner diameter 50mm, minimum diameter 25mm, height 2000mm, chuck internal diameter 80mm; Regulate the heating agent temperature in, making the temperature in the reactive crystallization pipe is 90～100 ℃; Reactive crystallization pipe bottom configuration plunger tpe barrier film oscillatory flow producer, oscillation frequency is 1～3Hz, amplitude 3～5mm; Gas-liquid-solid separator internal diameter 100mm, the outer setting heat exchange jacket, it is 100～105 ℃ that adjusting heating agent inlet temperature makes the liquidus temperature in the separator; The solid phase discharging mechanism adopts the bivalve type discharger; The reaction crystalizer working pressure is 0.15MPa.
The employing of preparation of raw material operation has the continuous stirred tank realization recycle stock of electrically heated wall and mixing of raw material hydrazine hydrate and urea, prepared materials by weight the percentage ratio meter to contain hydrazine hydrate 20%, urea 60%, surplus be water, add reaction crystalizer down at 100 ℃, feeding rate is 3000ml/h.
The ammonia separation circuit adopts the flash distillation bottle, atmospheric operation, and the ammonia steam of cat head is sent to and is used sulfuric acid absorption.
The solid-liquid separation circuit adopts vacuum filtration, filter cake clear water countercurrent washing three times.Filtrate and washings are delivered to the recycle of preparation of raw material operation, and the filter cake after the washing is the hydrazo-dicarbonamide product, can get the about 500g/h of hydrazo-dicarbonamide particle of the about 0.1mm of median size after the drying.
Claims (19)
1. the continuous production method of a synthetic hydrazo-dicarbonamide is characterized in that:
(1) adopting the pipe reaction crystallizer is reactive crystallization equipment, and hydrazine hydrate and urea soln are added the feed(raw material)inlet that is positioned at pipe reaction crystallizer middle and lower part continuously, and hydrazine hydrate and urea react in the pipe reaction crystallizer and crystallization generates the hydrazo-dicarbonamide particle;
(2) along with the carrying out that the hydrazo-dicarbonamide grain diameter increases gradually and, the hydrazo-dicarbonamide particle that is settled down to the reaction crystalizer bottom is discharged continuously of reaction crystallization process, obtain the hydrazo-dicarbonamide product through solid-liquid separation and washing again to the sedimentation of the bottom of reaction crystalizer;
(3) mother liquor that will contain unconverted reactant is discharged continuously from the top of reactor; Byproduct of reaction ammonia is discharged continuously from reactor head.
2. continuous production method according to claim 1 is characterized in that: add the hydrazine hydrate and the aqueous solution of urea of pipe reaction crystallizer feed(raw material)inlet in step (1), weight percent consists of hydrazine hydrate 4～40% and urea 10～60%.
3. continuous production method according to claim 2 is characterized in that: add the hydrazine hydrate and the aqueous solution of urea of pipe reaction crystallizer feed(raw material)inlet in step (1), weight percent consists of hydrazine hydrate 15～30% and urea 30～60%.
4. continuous production method according to claim 1 is characterized in that: the liquid phase material reuse that solid-liquid separation described in the step (2) and washing produce.
5. continuous production method according to claim 1 is characterized in that: the hydrazo-dicarbonamide particle that is settled down to the reaction crystalizer bottom in the step (2) is discharged continuously with slurry form, and the solid content of discharging slurry is 5%～70%.
6. continuous production method according to claim 1 is characterized in that: the mother liquor that contains unconverted reactant described in the step (3) is discharged the back reuse continuously from the top of reactor.
7. continuous production method according to claim 6 is characterized in that: the mother liquor that contains unconverted reactant reuse after dehydration procedure is sloughed part moisture of discharging continuously from the top of reactor.
8. continuous production method according to claim 1 is characterized in that: the hydrazine hydrate in the byproduct of reaction ammonia described in the step (3) is separated reuse.
9. pipe reaction crystallizer of implementing each described continuous production method of claim 1～8, comprise reactive crystallization pipe (1), it is characterized in that: described reactive crystallization pipe (1) is vertically arranged, the outside is provided with heat exchanger (12), reactive crystallization pipe (1) top is provided with gas-solid-liquid/gas separator (4), gas-solid-liquid/gas separator (4) side has the liquid phase discharge port (6) that is used to discharge the mother liquor that contains unconverted reactant, the top of gas-solid-liquid/gas separator (4) is provided with the gas phase discharge port (5) that is used to get rid of ammonia, reactive crystallization pipe (1) middle and lower part is provided with feed(raw material)inlet (2), reactive crystallization pipe (1) bottom is provided with and is used to discharge hydrazo-dicarbonamide particulate products export, and the position of reactive crystallization pipe (1) between feed(raw material)inlet (2) and products export is provided with oscillatory flow producer (10).
10. pipe reaction crystallizer according to claim 9 is characterized in that: have turbulent baffle in the described reactive crystallization pipe (1).
11. pipe reaction crystallizer according to claim 9 is characterized in that: described reactive crystallization pipe (1) is made into the interior cross-sectional area of order pipe and is periodically variable bellows-shaped.
12., it is characterized in that according to the described pipe reaction crystallizer of the arbitrary claim of claim 9-11: reactive crystallization pipe (1) length of described feed(raw material)inlet (2) below be feed(raw material)inlet (2) top reactive crystallization pipe (1) length 10%～60%.
13. pipe reaction crystallizer according to claim 12 is characterized in that: reactive crystallization pipe (1) length of described feed(raw material)inlet (2) below be feed(raw material)inlet (2) top reactive crystallization pipe (1) length 20%～40%.
14. the pipe reaction crystallizer according to the arbitrary claim of claim 9-11 is characterized in that: described gas-solid-liquid/gas separator is provided with traverse baffle or filter screen in (4).
15. pipe reaction crystallizer according to claim 9, it is characterized in that: the chuck that described heat exchanger (12) is provided with for segmentation, regulate the heating agent inlet temperature and the flow of every section chuck respectively, thereby the axial temperature in the control reaction crystalizer distributes.
16. according to claim 9 or 15 described pipe reaction crystallizers, it is characterized in that: axial temperature distributes 20～150 ℃ of scopes in the described reaction crystalizer.
17. pipe reaction crystallizer according to claim 16 is characterized in that: axial temperature distributes 80～130 ℃ of scopes in the described reaction crystalizer.
18. pipe reaction crystallizer according to claim 9 is characterized in that: the working pressure of described reaction crystalizer is at 0.1～0.5MPa.
19. pipe reaction crystallizer according to claim 9 is characterized in that: described oscillatory flow producer (10) is that 0.1～10Hz and amplitude are that the periodic swinging of 3～200mm flows in the inner frequency that produces of reaction crystalizer.
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| CN201010264112XA CN101967114B (en) | 2010-08-27 | 2010-08-27 | Continuous production method and continuous production device for synthesizing biruea |
| PCT/CN2011/078695 WO2012025038A1 (en) | 2010-08-27 | 2011-08-22 | Continuous manufacturing method and apparatus for synthesized hydazo dicarbonamide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012025038A1 (en) * | 2010-08-27 | 2012-03-01 | 浙江工程设计有限公司 | Continuous manufacturing method and apparatus for synthesized hydazo dicarbonamide |
| CN102399172A (en) * | 2011-09-22 | 2012-04-04 | 杭州海虹精细化工有限公司 | Process for producing biurea by combining acid-free condensation and acid-containing condensation |
| CN106866367A (en) * | 2017-04-17 | 2017-06-20 | 武汉科技大学 | A kind of continuous oscillation drift tube type crystallisation by cooling method of antierythrite |
| CN109529397A (en) * | 2018-12-28 | 2019-03-29 | 四川金象赛瑞化工股份有限公司 | One kind is sublimated crystallizer and method for crystallising |
| CN111377833A (en) * | 2018-12-29 | 2020-07-07 | 江西世龙实业股份有限公司 | Preparation method of AC foaming agent |
| WO2021056272A1 (en) * | 2019-09-25 | 2021-04-01 | 凯莱英生命科学技术(天津)有限公司 | Continuous gas-liquid reaction device and continuous gas-liquid reaction system including same |
Families Citing this family (2)
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| CN103044290A (en) * | 2013-01-08 | 2013-04-17 | 杭州海虹精细化工有限公司 | Method for increasing reaction speed in preparing biurea by condensing with weak base method |
| CN106008278B (en) * | 2016-06-06 | 2017-12-19 | 青海盐湖工业股份有限公司 | A kind of preparation method of biruea |
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| CN101967114B (en) * | 2010-08-27 | 2013-07-03 | 浙江工程设计有限公司 | Continuous production method and continuous production device for synthesizing biruea |
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| CN1958143A (en) * | 2006-09-29 | 2007-05-09 | 浙江大学 | Oscillatory flow tubular reactor of balking ring baffle |
| CN1958144A (en) * | 2006-09-29 | 2007-05-09 | 浙江大学 | Oscillatory flow tubular reactor with ripple wall |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012025038A1 (en) * | 2010-08-27 | 2012-03-01 | 浙江工程设计有限公司 | Continuous manufacturing method and apparatus for synthesized hydazo dicarbonamide |
| CN102399172A (en) * | 2011-09-22 | 2012-04-04 | 杭州海虹精细化工有限公司 | Process for producing biurea by combining acid-free condensation and acid-containing condensation |
| CN106866367A (en) * | 2017-04-17 | 2017-06-20 | 武汉科技大学 | A kind of continuous oscillation drift tube type crystallisation by cooling method of antierythrite |
| CN109529397A (en) * | 2018-12-28 | 2019-03-29 | 四川金象赛瑞化工股份有限公司 | One kind is sublimated crystallizer and method for crystallising |
| CN109529397B (en) * | 2018-12-28 | 2024-07-02 | 四川金象赛瑞化工股份有限公司 | De-sublimation crystallization equipment and crystallization method |
| CN111377833A (en) * | 2018-12-29 | 2020-07-07 | 江西世龙实业股份有限公司 | Preparation method of AC foaming agent |
| CN111377833B (en) * | 2018-12-29 | 2022-05-20 | 江西世龙实业股份有限公司 | Preparation method of AC foaming agent |
| WO2021056272A1 (en) * | 2019-09-25 | 2021-04-01 | 凯莱英生命科学技术(天津)有限公司 | Continuous gas-liquid reaction device and continuous gas-liquid reaction system including same |
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| WO2012025038A1 (en) | 2012-03-01 |
| CN101967114B (en) | 2013-07-03 |
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