CN103755599A - Preparation process of azodicarbonamide - Google Patents
Preparation process of azodicarbonamide Download PDFInfo
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- CN103755599A CN103755599A CN201310720602.XA CN201310720602A CN103755599A CN 103755599 A CN103755599 A CN 103755599A CN 201310720602 A CN201310720602 A CN 201310720602A CN 103755599 A CN103755599 A CN 103755599A
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Abstract
The invention discloses a preparation process of azodicarbonamide. The process comprises the steps: 1) synthesizing a hydrazine hydrate crude product by a urea method; 2) refining hydrazine hydrate by a freeze separation method; 3) preparing biurea by alkaline condensation; and 4) obtaining the azodicarbonamide by a hydrogen peroxide oxidation method. According to the preparation process, different procedure production methods are analyzed and compared, the hydrazine hydrate is synthesized by selecting the urea method; refined hydrazine is obtained from crude hydrazine by the freeze separation method, biurea is prepared in a continuous condensation manner by an alkaline process, and finally, the azodicarbonamide is generated by the biurea oxidized by the hydrogen peroxide. Thus, the traditional acid condensation is changed into alkaline condensation to synthesize the biurea, consumption of raw materials and environmental pollution are reduced, hydrogen peroxide is selected as an oxidant in the oxidation process of the biurea, just by-product water is generated in the reaction, the environment is not polluted, and a green chemical pathway is taken.
Description
Technical field
The present invention relates to a kind of preparation technology of Cellmic C 121.
Background technology
The production technique of Cellmic C 121 is divided into four parts: synthetic, the thick hydrazine of hydrazine hydrate is refining, condensation reaction and hydrazo-dicarbonamide oxidation.It is oxygenant that most of manufacturers adopt chlorine while producing hydrazine raw material with Wyler's process, while producing ADC with hydrazo-dicarbonamide, also with chlorine, makes oxygenant.Unreacted chlorine enters atmosphere, contaminate environment.Along with national and society more and more pay attention to environment protection, to using the pressure of chlorine and limiting increasing, tackle existing technique for this reason and improve, as being raw material with ketazine, with hydrogen peroxide, replace chlorine to make oxygenant etc.
One, current, hydrazine hydrate production technique mainly contains five kinds both at home and abroad: traditional La Xifa (Raschig method), Wyler's process, ketazine process, dioxygen water law (PCUK method) and air oxidation process etc.
(1) La Xifa (Raschig method) is 1906, by German Raschig, is proposed to take ammonia as nitrogenous source, with hypochlorite oxidation ammonia, becomes hydrazine hydrate.In this reaction process, there is chloramines to generate, therefore also referred to as chloramine method.This is the most ancient method of industrial production hydrazine.The sodium hydroxide that this method is is 8% with excessive massfraction and chlorine reaction generate clorox.Ammonia and chlorine bleach liquor's ratio of mixture is 20:1, and temperature of reaction is 170 ℃, and under pressurized conditions, reaction just can complete within the several seconds.In reactive system, add gelatin, can improve productive rate.Raschig process obtains is rare hydrazine solution of 1%～4%, and total recovery is about 67%, and the dilute solution of concentrated hydrazine needs considerable heat, and ammonia is excessive, needs retrieving arrangement, produces a large amount of salt by-product.The shortcomings such as Given this method environmental pollution is serious, and facility investment is large, and product yield is low, are eliminated at present substantially.
(2) this method of Wyler's process is that chlorine bleach liquor and urea are prepared hydrazine hydrate by a certain percentage under magnesium sulfate catalyst action.Reaction obtained the thick hydrazine that hydrazine content is greater than 2% before this, through vacuum distilling, removed a large amount of salt impurity, obtained 6% hydrazine hydrate, then obtained approximately 40% hydrazine hydrate through evaporation concentration.Because clorox is strong oxidizer, hydrazine hydrate is strong reductant, when batching at that time following side reaction can not occur:
N
2H
4·H
2O+2NaCIO→N
2↑+2NaCI+3H
2O
This side reaction is violent, and in production, ingredient proportion is not noted material spray accident may occur.Owing to producing a large amount of byproduct Sodium carbonate decahydrates and sodium-chlor in Wyler's process production process, can not recycle, and hydrazine yield is not high especially, external basic other the method that adopts replaces.But the technique of this method is simple, easy to operate, domestic majority still adopts this method.For deficiency and the shortcoming of Wyler's process, the manufacturing enterprise of China constantly carries out process modification, suppresses the generation of side reaction, improves the yield of hydrazine hydrate, recycles byproduct, reduces production costs.
(3) first this method of ketazine process is proposed by German Bayer company the sixties in 20th century, and realizes abroad industrialization the seventies.Ketazine process is that by clorox and ammonia react, the ketazine intermediate product of generation is under high pressure hydrolyzed to hydrazine hydrate under ketone exists.Compare with Raschig process, ketazine process less investment, product yield are high, less energy consumption, cost are low, but this method is serious to equipment corrosion, and product separation is difficult, and environment has chlorine pollution.Because ketazine is relatively stable, so the concentration of reaction product can improve, and in rare hydrazine solution of hydrolysis gained, the content of hydrazine can be brought up to more than 10%, evaporation Energy Intensity Reduction.
(4) hydrogen peroxide method is 1970, and France starts to substitute with hydrogen peroxide the research that clorox is made the synthetic hydrazine of oxygenant.Hydrogen peroxide method is that butanone and ammonia generate ketoimine under catalyzer exists, and ketoimine generates butanone azine after hydrogen peroxide is oxidized to the different hydrazone of oxa-, and butanone azine is hydrolyzed into hydrazine hydrate and butanone again.The butanone generating can recycle.
Hydrogen peroxide method is the improvement to ketazine process, and oxygenant is selected hydrogen peroxide, has avoided a large amount of by-product salt with clorox generation, and technique is more clean, and external most of manufacturers adopt this method at present.But in product, organic content exceeds nearly a hundred times than Wyler's process.With ketazine process comparison, although the cost ratio acetone of butanone is high, the intermediate product butanone azine and the water that generate do not dissolve each other, separated simple, needn't carry out rectifying, if standing separation, therefore can reduce energy consumption.
(5) air oxidation process air oxidation process is state-of-the-art a kind of in hydrazine method processed at present, basic raw material is only ammonia and air, other raw materials can be recycled as benzophenone, cuprous chloride etc. in building-up process, and all belong to the chemical that is easy to get, but this method is difficult to realize suitability for industrialized production.
Two, thick hydrazine treating process
The thick hydrazine hydrate of being produced by clorox and urea solution method, hydrazine hydrate content, only in 4% left and right, wherein also contains the impurity such as a large amount of sodium carbonate, sodium-chlor.These sodium carbonate are present in thick hydrazine hydrate solution with the form of Sodium carbonate decahydrate, and sodium carbonate accounts for 10% left and right of total composition.A large amount of sodium carbonate exists, and it is unfavorable that ADC whipping agent is produced, and can consume in sulfuric acid and reaction morely and produce a large amount of carbon dioxide gass, to environment.The main calcium chloride cold method that adopts reclaims Sodium carbonate decahydrate at present, according to the content of sodium carbonate in thick hydrazine, in thick hydrazine, add appropriate calcium chloride, calcium chloride and sodium carbonate generation disproportionation reaction generate calcium carbonate, calcium carbonate easily precipitates, material layering in storage tank is obvious, and supernatant liquor directly goes condensation, and bottom throw out is sent from scheming and isolates calcium carbonate.
Three, condensation reaction
Hydrazo-dicarbonamide technique is produced in condensation reaction both at home and abroad at present three kinds: acid condensation, anacidity condensation and alkaline condensation.Each method is compared as follows:
(1) company that the acid condensation of acid condensation is produced thick hydrazine hydrate by domestic Wyler's process is widely used, the inorganic ammonium salt such as a large amount of ammonium sulfate of by-product and ammonium chloride when adopting acid condensation process to obtain hydrazo-dicarbonamide, make the ammonia-nitrogen content of condensed mother liquor and washings very high, and the inorganic salts such as sodium-chlor owing to containing thick hydrazine solution and bring into, cause mother liquor and washings to be difficult to ammonia nitrogen to be down to emission standard by general processing means.Its advantage is that the condensation time is short, and plant factor is high, and shortcoming is that condensed mother liquor and high density washing water are high saliferous high ammonia-nitrogen wastewater, and processing cost is high.Acid system speed of response is fast, and energy consumption is low, and reaction yield is all more than 90%, but this method need react under strong acid condition, large to the corrodibility of equipment, the having relatively high expectations of equipment, and reaction can produce a large amount of acid waste water, seriously polluted to environment.
(2) condensation of anacidity condensation anacidity is applicable to pure hydrazine and urea condensation, can realize the recycling of ammonia and the recycle to extinction of condensed mother liquor in its production process, generally adopts this technique abroad.The refining hydrazine hydrate that adopts Wyler's process to obtain is poured in condensation kettle, and urea solid is poured in reactor, guarantees that effective hydrazine composition and weight of urea ratio are 0.21-0.27, controls temperature of reaction 115-125 ℃, reaction 8-10h.Still material filters, and washing, obtains hydrazo-dicarbonamide solid.Utilize 10% pure hydrazine hydrate as condensation raw material, changing traditional acid condensation is anacidity condensation.
Adopt continuous anacidity condensation process, with not containing pure hydrazine hydrate solution and the urea reaction of inorganic salt impurity, do not add other catalyzer, rely on process control that reaction is carried out according to processing requirement.Reaction process serialization, improves production capacity greatly, and what is more important realizes the recycle to extinction of condensation reaction mother liquor.Hydrazo-dicarbonamide wet basis is directly produced for oxidation without washing, the discharge of having stopped ammonia nitrogen waste water, and the ammonia nitrogen waste water that solves condensation operation is processed a difficult problem.Condensation reaction device does not change itself, only carries out the improvement of tail gas draw-out device, improves tail gas Extracting Ability and makes it to adapt to anacidity condensation production, increases liquefied ammonia retrieving arrangement, by the ammonia remanufacture liquefied ammonia in condensation tail gas.
(3) alkaline condensation alkaline condensation is suitable for the higher hydrazine hydrate that does not contain water-soluble inorganic salt and alkali of purity of ketazine process and the production of dioxygen water law.Therefore, there is Lewis substitution reaction in hydrazine hydrate and urea under the applicable condition of temperature, and subtraction is produced hydrazo-dicarbonamide.
The advantage that this method is produced hydrazo-dicarbonamide has: (1) hydrazo-dicarbonamide purity is high, not contains sodium sulfate class impurity; (2) washing water return to hydrazine hydrate upgrading tower, do not produce washes; (3) under alkaline condition, carry out obtaining condensation reaction, condensation kettle requirement for anticorrosion grade reduces greatly, extends several times and even ten times the work-ing life of equipment.But also exist speed of response slow, long reaction time, the shortcoming such as plant factor is low, and steam consumption is large, high expensive.
Four, oxidizing reaction
Oxidation production technique mainly contains four kinds both at home and abroad at present, by the difference of oxygenant used, can be divided into chromate process, chlorate process, chlorine method and hydrogen peroxide method.And the chromate process adopting is the earliest eliminated compared with producing pollution of chromium in high and production process because of cost.Chlorate process and chlorine method successively come across the initial stage the 60's of 20th century.Chlorate process is easy to operate, and reaction end is easy to control, but cost is high, and equipment corrosion is serious, after be eliminated gradually.Chlorine oxidation is had chlor-alkali device ADC enterprise because production cost is low extensively adopts, and its shortcoming is in by-product, to have a large amount of hydrochloric acid to deal carefully with.Hydrogen peroxide oxidation reaction end is easy to control, and can realize recycling of mother liquor, and discharge spent acid amount is few.Its shortcoming is that system corrodibility is strong, and high to pipeline and equipment requirements, production cost is higher than chlorine oxidation process.There is fewer companies to adopt high density (>=50%) hydrogen peroxide as oxidant abroad, realized the recycle to extinction of mother liquor.Below mainly compare chlorate process, chlorine method and these three kinds of methods of hydrogen peroxide method.
(1) sodium chlorate oxidation
Reaction is carried out under acidic conditions.Ammonium meta-vanadate and arene sulfonate for catalyzer, yield 93% ~ 94%; With Sodium Bromide, 37.5 ℃ of temperature, yield 98%; With tin anhydride, 38 ~ 40 ℃, yield 96.6%, purity 99.8%; With vanadium complexes, 60% ~ 75%, yield 95%, Chun Du≤99%.Sodium chlorate consumption approaches theoretical amount, and reaction end 1mol hydrazo-dicarbonamide easy to control only needs 1/3mol sodium chlorate.Sodium chlorate is solid, and storing is convenient, but price is higher, still difficult industrialization.
(2) chlorine oxidation
With Sodium Bromide or bromine as catalyzer, anti-Ying Wendu≤50 ℃, yield 90% ~ 94%, purity > 98.5%[13].Use additive and control proper high purity, high gas forming amount, fine particle (average out to 3 μ m) and the narrow high-quality product of distribution range of obtaining.Logical chlorine can not be excessive, otherwise cause that ADC decomposes.Adopt chlorine oxidation process, the waste liquid of ADC mother liquor and washings is the hydrochloric acid of concentration 10% ~ 20%.In this hydrochloric acid, contain a large amount of inorganic salt and organic amine and azo material, be difficult to process.This process costs is low, for the most of producers in the world adopt, but has spent acid to generate and the chlorine effusion for reacting, contaminate environment.China's oxidation hydrazo-dicarbonamide is the chlorine that adopts while preparing whipping agent ADC more, produces a large amount of hydrochloric acid byproducts, and environment is caused to serious pollution, and waste resource.
(3) hydrogen peroxide oxidation
Catalyzer is bromine, and (according to the seventies, rely on the patent literature that external relevant hydrogen peroxide is prepared Cellmic C 121, reaction is at Br
-ion and mineral acid react 1.5～3.0 hours under existing at 25 ~ 55 ℃, can obtain 96.1 ~ 98.7% yield, and purity is more than 98%.15 ~ 55 ℃ of temperature of reaction, yield 96.1%, purity 98.7%.
Oxygen water consumption is close to theoretical value, and reaction end is easy to control.Quality product is better than logical chlorine method, is the friendly process that cost is higher.Su Bingjun, Yang Ji and and the people such as Zhou Nianzu in 1984, point out in the literature, at Br
-ionic concn is 1.7%, and inorganic acid salt acid concentration is 7%, and hydrogen peroxide and hydrazo-dicarbonamide proportioning are 1:1.05, and temperature of reaction is controlled at 44～54 ℃, the product yield under above condition: 98.4～98.9%; Purity 99.7～100%.
Compare with chlorine method, hydrogen peroxide method is more easy to control, and product yield is high, steady quality; But in reaction, need to provide acidic medium, along with the carrying out of reaction and adding of hydrogen peroxide, the acidity of medium reduces gradually; Because chlorine is not used in reaction, the decomposition of the effusion of excessive chlorine and ADC finished product while having avoided terminal, has improved yield and has alleviated again the pollution to environment.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing defect, and the preparation technology of a kind of environmentally safe, productive rate is high, cost is low Cellmic C 121 is provided.
Object of the present invention is carried out specific implementation by the following technical programs:
A preparation technology for Cellmic C 121, comprises the steps:
1) Wyler's process oxo-synthesis of hydrazine hydrate crude product
Clorox, sodium hydroxide solution and urea soln are mixed, and under the katalysis of magnesium sulfate, reaction at 110-114 ℃, obtains the crude product of hydrazine hydrate,
Wherein, the mass ratio of urea and clorox is 1:1.189, and the mass ratio of clorox and sodium hydroxide is 1:1.162;
2) the refining hydrazine hydrate of subzero fractionation method
By the crude product frozen cooling of the resulting hydrazine hydrate of step 1), to-5 ℃, the impurity sodium carbonate of the crude product of hydrazine hydrate is separated out with the solid form of Sodium carbonate decahydrate crystallization, separated except sodium carbonate, obtains rough hydrazine hydrate;
3) alkaline process condensation hydrazo-dicarbonamide processed
By step 2) in resulting refining hydrazine hydrate solution and urea amine 1:3
.9 weight ratio is mixed, and regulates pH at 7-10, controls temperature of reaction more than 100 ℃, obtains hydrazo-dicarbonamide and by product thereof after condensation reaction, is separated by filtration, washs, and obtains hydrazo-dicarbonamide;
4) hydrogen peroxide oxidation process obtains Cellmic C 121
In the hydrazo-dicarbonamide obtaining to step 3), add superoxol, the weight ratio of hydrazo-dicarbonamide and hydrogen peroxide is 1:1.15, under the effect of catalyzer Sodium Bromide and promotor Vanadium Pentoxide in FLAKES, reacts 2-2.5 hour at 44-50 ℃, generates Cellmic C 121.
Preferably, in step 1), the mass concentration of described sodium hydroxide solution is 11%, and urea soln mass concentration is 4%; The add-on of described magnesium sulfate is 1 with the mass ratio that reacts urea used
:83
.33.
Preferably, in step 3),
The consumption of described catalyzer Sodium Bromide and promotor Vanadium Pentoxide in FLAKES is all 1% of hydrazo-dicarbonamide quality;
Adopt sulphur acid for adjusting pH value;
Adopt vapor heated method to control temperature of reaction more than 100 ℃.
Beneficial effect of the present invention:
The present invention, by analyzing each more different operation production methods, selects to use Wyler's process oxo-synthesis of hydrazine hydrate, and thick hydrazine obtains smart hydrazine by subzero fractionation, through alkaline process continuous condensating, produces hydrazo-dicarbonamide, finally with hydrogen peroxide oxidation hydrazo-dicarbonamide, generates Cellmic C 121.The acid system condensation of abandoning tradition makes the synthetic hydrazo-dicarbonamide of alkaline process condensation into, has reduced consumption and the pollution to environment of raw material; In hydrazo-dicarbonamide oxidising process, select hydrogen peroxide as oxygenant, reaction only generates water byproduct, free from environmental pollution, walks green chemical industry road.
In addition, the present invention has broken traditional strict material ratio, in thick hydrazine preparation, select urine chlorine than 1:1.189, chlor-alkali than 1:1.162, can realize hydrazine hydrate content in thick hydrazine and reach 50.34kg/m3, the transformation efficiency of urea is 74%.In condensation reaction, hydrazine hydrate solution and urea soln proportioning (mass ratio) are: 1:3.9, the yield of hydrazo-dicarbonamide reaches 97%.In hydrazo-dicarbonamide oxidizing reaction, mole proportioning of hydrazo-dicarbonamide and hydrogen peroxide is: 1:1.15, and the yield of ADC is 98%, purity is 99%.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, for explaining the present invention, is not construed as limiting the invention together with embodiments of the present invention.In the accompanying drawings:
Fig. 1 is preparation technology's schema of Cellmic C 121 of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
embodiment 1:
The preparation technology of Cellmic C 121, technical process is referring to Fig. 1, and step is as follows:
1) urea soln that is 4% by clorox, sodium hydroxide lye that mass concentration is 11% and the mass concentration for preparing compares 1:1 by urine chlorine
.189(mass ratio), chlor-alkali is than for 1:1.162(mass ratio) by pump delivery to riser reactor, in catalyzer add-on, be 1 with reacting urea quality ratio used
:83
.under the effect of 33 magnesium sulfate, produce hydrazine hydrate, pipeline reactor temperature of reaction is controlled at 110～114 ℃, obtains hydrazine hydrate solution (crude product).
2) hydrazine hydrate solution generating is through frozen cooling to-5 ℃, and sodium carbonate is separated out with the solid form of Sodium carbonate decahydrate crystallization, sends into whizzer and carries out solid-liquid separation and remove salt, and it is that next process is used that refining hydrazine hydrate is sent into dosing vessel.
3) refining hydrazine hydrate solution is with being pumped into condensation kettle, by the raw material weight of hydrazine hydrate and urea, than 1:3.9, add the urea soln configuring to be squeezed in condensation reaction still by pump, with sulfuric acid, regulate the pH of reaction between 7 ~ 10, make reaction soln keep weakly alkaline, by steam heating temperature, be controlled at and be greater than 100 ℃ and carry out continuity condensation reaction, make hydrazo-dicarbonamide and by product thereof, be separated by filtration, wash, obtain hydrazo-dicarbonamide.
4) hydrazo-dicarbonamide is sent into stills for air blowing, by 1:1.15(mass ratio) proportioning add superoxol, at consumption, be all under 1% Sodium Bromide catalyzer and the effect of Vanadium Pentoxide in FLAKES promotor of hydrazo-dicarbonamide quality, temperature of reaction is controlled at 44～50 ℃ and carries out oxidizing reaction 2 ~ 2.5 hours, generate Cellmic C 121, then through washing, centrifugation, obtaining liquid is oxidation mother liquor, and solid is wet ADC whipping agent.Wet ADC whipping agent, enters cyclonic separator and carries out separation with warm air after air stream drying, gets final product to obtain finished product.
The technical requirements of whipping agent ADC sees the following form:
Note: median size is consulted index for user; Purity index is sampling observation index.
The resulting ADC whipping agent of the inventive method all meets the requirement of premium grads.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. a preparation technology for Cellmic C 121, is characterized in that: comprise the steps:
Wyler's process oxo-synthesis of hydrazine hydrate crude product
Clorox, sodium hydroxide solution and urea soln are mixed, and under the katalysis of magnesium sulfate, reaction at 110-114 ℃, obtains the crude product of hydrazine hydrate,
Wherein, the mass ratio of urea and clorox is 1:1.189, and the mass ratio of clorox and sodium hydroxide is 1:1.162;
2) the refining hydrazine hydrate of subzero fractionation method
By the crude product frozen cooling of the resulting hydrazine hydrate of step 1), to-5 ℃, the impurity sodium carbonate of the crude product of hydrazine hydrate is separated out with the solid form of Sodium carbonate decahydrate crystallization, separated except sodium carbonate, obtains refining hydrazine hydrate solution;
3) alkaline process condensation hydrazo-dicarbonamide processed
By step 2) in resulting refining hydrazine hydrate solution and urea press 1:3
.9 weight ratio is mixed, and regulates pH at 7-10, controls temperature of reaction more than 100 ℃, obtains hydrazo-dicarbonamide and by product thereof after condensation reaction, is separated by filtration, washs, and obtains hydrazo-dicarbonamide;
4) hydrogen peroxide oxidation process obtains Cellmic C 121
In the hydrazo-dicarbonamide obtaining to step 3), add superoxol, the weight ratio of hydrazo-dicarbonamide and hydrogen peroxide is 1:1.15, under the effect of catalyzer Sodium Bromide and promotor Vanadium Pentoxide in FLAKES, reacts 2-2.5 hour at 44-50 ℃, generates Cellmic C 121.
2. the preparation technology of Cellmic C 121 according to claim 1, is characterized in that: in step 1), the mass concentration of described sodium hydroxide solution is 11%, and urea soln mass concentration is 4%.
3. the preparation technology of Cellmic C 121 according to claim 1, is characterized in that: in step 1), the add-on of described magnesium sulfate is 1:83.33 with the mass ratio that reacts urea used.
4. the preparation technology of Cellmic C 121 according to claim 1, is characterized in that: in step 3), the consumption of described catalyzer Sodium Bromide and promotor Vanadium Pentoxide in FLAKES is all 1% of hydrazo-dicarbonamide quality.
5. the preparation technology of Cellmic C 121 according to claim 1, is characterized in that: in step 3), adopt sulphur acid for adjusting pH value.
6. the preparation technology of Cellmic C 121 according to claim 1, is characterized in that: in step 3), adopt vapor heated method to control temperature of reaction more than 100 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104761472A (en) * | 2015-03-04 | 2015-07-08 | 杭州海虹精细化工有限公司 | Technology for clean preparation of biurea with high efficiency and low consumption |
| CN106748896A (en) * | 2015-11-25 | 2017-05-31 | 衡阳市锦轩化工有限公司 | A kind of synthetic method of ADC |
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| CN1803899A (en) * | 2005-12-27 | 2006-07-19 | 薛式华 | Method for preparing AC blowing agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104761472A (en) * | 2015-03-04 | 2015-07-08 | 杭州海虹精细化工有限公司 | Technology for clean preparation of biurea with high efficiency and low consumption |
| CN104761472B (en) * | 2015-03-04 | 2016-08-24 | 杭州海虹精细化工有限公司 | The technique that a kind of efficient low-consume cleaning prepares biruea |
| CN106748896A (en) * | 2015-11-25 | 2017-05-31 | 衡阳市锦轩化工有限公司 | A kind of synthetic method of ADC |
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Application publication date: 20140430 |