CN104761472A - Technology for clean preparation of biurea with high efficiency and low consumption - Google Patents
Technology for clean preparation of biurea with high efficiency and low consumption Download PDFInfo
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- CN104761472A CN104761472A CN201510096097.5A CN201510096097A CN104761472A CN 104761472 A CN104761472 A CN 104761472A CN 201510096097 A CN201510096097 A CN 201510096097A CN 104761472 A CN104761472 A CN 104761472A
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- dicarbonamide
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Abstract
The invention relates to a technology for clean preparation of biurea with high efficiency and low consumption. The technology includes: mixing a urea solution with a hypochlorite solution containing excessive strong base, and controlling the reaction temperature; pumping the mixed materials into a tubular heat exchanger, and performing rapid heating; rapidly raising the temperature of the material obtained in step b to 130DEG C-180DEG C; keeping the temperature, performing pressurizing and maintaining a constant temperature till condensation; at the end of reaction, conducting cooling, adding acid into the reaction solution, and adjusting the pH value, thus finishing the reaction; and carrying out filtering, washing and drying, thus obtaining the biurea solid. The technology provided by the invention avoids replenishing urea and a series of tedious processes in the prior art, greatly reduces the power consumption and steam consumption in the processes, also reduces the loss of caustic soda, chlorine and urea, lowers the product cost, increases the product yield, and recovers ammonia and carbon dioxide with higher added value. After appropriate conventional treatment, biurea can be reused as a raw material in manufacturing caustic soda chlorine, and the pollution problem of ammonia-nitrogen wastewater can be eliminated.
Description
Technical field
The present invention relates to the method for producing hydrazo-dicarbonamide, be specifically related to a kind of efficient low-consume and clean the technique preparing hydrazo-dicarbonamide.
Background technology
The chemical name of hydrazo-dicarbonamide is hydrazo diformamide, and molecular formula is C
2h
6n
4o
2, chemical formula is H
2nCONH-NHCONH
2, relative molecular mass is 118.It is mainly used in the production of ADC whipping agent (Cellmic C 121), also can be used for airstrip, super highway, gear anti-skidding, the back-fire relief of high degree cable is anti-molten.
Hydrazo-dicarbonamide normally carries out condensation reaction generation in acid condition by hydrazine hydrate and urea.This explained hereafter hydrazo-dicarbonamide, one of its raw material is hydrazine hydrate, preparation method's more complicated of hydrazine hydrate, and conventional method is urea oxidation style and ketazine process.Domestic basic employing urea oxidation style, namely adopt NaClO to be oxidized urea and produce the hydrazine hydrate solution that content is 4 ~ 6%, again by freezing, de-Sodium carbonate decahydrate, after this step, a kind of technique is carried out concentrate, refines to prepare hydrazine hydrate, the hydrazine hydrate generated reacts with urea condensation again, generates hydrazo-dicarbonamide product, by-product ammoniacal liquor.Technical process is longer, production technique relative complex, and energy consumption is very high.And the sodium carbonate of by-product is as useless solid, added value is very low, and containing ammonium chloride, sodium-chlor etc., complicated component.Another kind of technique adopts rare hydrazine hydrate and urea to carry out acid adding condensation to prepare hydrazo-dicarbonamide, the then ammonium salt of a large amount of high density and sodium chloride salt discharge in mother liquor, seriously polluted, process then cost very high, and high concentration salts sewage discharge problem will be produced, causing substantial pollution to environment, is the large problem perplexing whole ADC industry.Above-mentioned two kinds of method yields are not very high, and in clorox, the yield of hydrazo-dicarbonamide is generally no more than 65%, only have about 50% with ureometer hydrazo-dicarbonamide yield.
Ketazine process is produced the first step hydrazine hydrate production of hydrazo-dicarbonamide and is also existed and comprise that acetone danger is high, inflammable and explosive, have the shortcomings such as organic substance residues in product hydrazine hydrate, the simultaneously hydrolysis of production process, evaporation, the flow process such as concentrated also need to consume a large amount of steam, hydrazine hydrate per ton approximately needs 25 tons of steam, belongs to high energy consumption production technique.
Summary of the invention
Object of the present invention is just in order to overcome the deficiency of above-mentioned technology, and provide a kind of efficient low-consume to clean the technique preparing hydrazo-dicarbonamide, by the synthesis mechanism of further investigation hydrazo-dicarbonamide reaction, the urea of Wyler's process hydrazine hydrate process by-product sodium carbonate and setting that allows of novelty continues to react, hydrazo-dicarbonamide and sodium-chlor can be generated by direct reaction again by acid adding, the production of sodium chloride salt Water circulation and caustic soda chlorine, and reclaim ammonia and carbonic acid gas two kinds comparatively high value-added product simultaneously, evade the last handling process that hydrazine hydrate production is a large amount of, considerably reduce cost, improve product yield and product purity, reduce the post-processing difficulty of factory effluent, it is a revolutionary efficient low-consume new cleanproduction process.
The object of the invention is to have come by following technical solution.This efficient low-consume cleans the technique preparing hydrazo-dicarbonamide, and this technique comprises following step:
A. by the urea soln that configures and the hypochlorite solutions containing excessive highly basic, according to urea: hypochlorite: the mol ratio of highly basic is that the ratio of 3-4:1:2-2.5 adds mixing tank mixing, and mixing process controls temperature of reaction 0 DEG C-30 DEG C;
B. mixed material pumping is in tubular heat exchange, is heated rapidly to 100 DEG C-130 DEG C;
C. proceed in the reactor that with pressure, band stirs through the material of b step, be rapidly heated 130 DEG C-180 DEG C further;
D., under keeping 130 DEG C of-180 DEG C of temperature condition, pressurization constant temperature 1 ~ 8h, until condensing reflux mouth no longer produces ammonia;
E. after reaction terminates, cool to 20 DEG C-60 DEG C, acid adding in reaction solution, adjustment pH value is 4-7, and reaction terminates;
F. filter, wash, dry and can obtain hydrazo-dicarbonamide solid.
As preferably, described hypochlorite and highly basic are respectively clorox and sodium hydroxide, or potassium hypochlorite and potassium hydroxide, or Losantin and calcium hydroxide.
As preferably, regulate the organic or inorganic acid that the acid of pH value is hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid or acidity are greater than carbonic acid in described step e, pH value is preferably adjusted to 5-6.
As preferably, urea in described a step drops at twice, first in a step, add urea: hypochlorite: the mol ratio of highly basic is the urea amount of 1-1.3:1:2-2.5, the urea of residue mole number adds in Step d, and the mol ratio of total urea, clorox, caustic soda is constant.
As preferably, when configuring urea soln, add the magnesium chloride of the 0.5%-2% of solution quality as protective material.
As preferably, in described Step d, temperature is preferably 140 DEG C-160 DEG C.
Beneficial effect of the present invention is: the present invention is by changing urea addition, by urea and clorox single step reaction, hydrazo-dicarbonamide is generated under acid adding condition, without by-product sodium carbonate in process, avoid the freezing of hydrazine hydrate in existing technique and remove sodium carbonate, evaporate, concentrate, again supplement a series of complicated processes such as urea, greatly reduce power consumptions a large amount of in these processes, steam consumption.By the reduction of reaction process, decrease the loss of caustic soda, chlorine and urea.Above-mentioned two changes considerably reduce product cost, improve the yield of product, reclaimed the higher ammonia of added value and carbonic acid gas, hydrazo-dicarbonamide mother liquor composition becomes comparatively single sodium chloride brine simultaneously, can be back to the manufacture raw material of caustic soda chlorine after suitable conventional processing as raw material.Eliminate ammonia nitrogen waste water pollution problem.This is a kind of revolutionary brand-new technique.
Embodiment
Below by embodiment, the present invention is further elaborated, and help is understood the present invention by embodiment better, but the present invention is not limited only to following embodiment.
This efficient low-consume of the present invention cleans the technique preparing hydrazo-dicarbonamide, and this technique comprises following step:
G. by the urea soln that configures and the hypochlorite solutions containing excessive highly basic, according to urea: hypochlorite: the mol ratio of highly basic is that the ratio of 3-4:1:2-2.5 adds mixing tank mixing, and mixing process controls temperature of reaction 0 DEG C-30 DEG C;
H. mixed material pumping is in tubular heat exchange, is heated rapidly to 100 DEG C-130 DEG C;
I. proceed in the reactor that with pressure, band stirs through the material of b step, be rapidly heated 130 DEG C-180 DEG C further;
J., under keeping 130 DEG C of-180 DEG C of temperature condition, pressurization constant temperature 1 ~ 8h, until condensing reflux mouth no longer produces ammonia;
K. after reaction terminates, cool to 20 DEG C-60 DEG C, acid adding in reaction solution, adjustment pH value is 4-7, and reaction terminates;
L. filter, wash, dry and can obtain hydrazo-dicarbonamide solid, NH
3with CO
2can utilize according to a conventional method.
As preferably, described hypochlorite and highly basic are respectively clorox and sodium hydroxide, or potassium hypochlorite and potassium hydroxide, or Losantin and calcium hydroxide, the preferred clorox of the present invention, sodium hydroxide.
As preferably, regulate the organic or inorganic acid that the acid of pH value is hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid or acidity are greater than carbonic acid in described step e, the preferred hydrochloric acid of the present invention, be beneficial to final by-product and only have a kind of composition of sodium-chlor, the sodium-chlor of by-product is beneficial to reclaim and uses, and pH value is preferably adjusted to 5-6.
As preferably, the urea in described a step once drops into; Or the urea in described a step drops at twice, first in a step, add urea: hypochlorite: the mol ratio of highly basic is the urea amount of 1-1.3:1:2-2.5, the urea of residue mole number adds in Step d, and the mol ratio of total urea, clorox, caustic soda is constant.The method of the preferred disposable input of the present invention.
As preferably, when configuring urea soln, add the magnesium chloride of the 0.5%-2% of solution quality as protective material.
As preferably, in described Step d, temperature is preferably 140 DEG C-160 DEG C.
Embodiment 1-4:
Take A urea, add suitable quantity of water and be configured to the urea soln that urea content is 400g/l, and add 0.5% magnesium chloride as protective material, for subsequent use after dissolving completely; Get the chlorine bleach liquor 100g that available chlorine content is B, add part sheet alkali wherein and make wherein containing excessive caustic soda C, for subsequent use;
By volume pump, two kinds of feed liquids are added mixing tank in proportion simultaneously to mix rapidly, mixing process temperature controls at D DEG C, and is pumped in tubular heat exchange, be heated to E DEG C rapidly, liquid after heating directly proceed to pressure, band stir reactor in, continue to be warmed up to F DEG C, until condensation exhaust mouth does not have ammonia to overflow after testing, record constant temperature time is about G, pressure release, cool to H, in reactor, drip hydrochloric acid, in dropping process, have bubble and white precipitate to separate out, to pH value to I, reaction terminates.Filter, washing, drying, by analysis, white depositions decomposition temperature is 248 DEG C, and be hydrazo-dicarbonamide, oven dry is weighed, and obtains hydrazo-dicarbonamide solid J, is K by the available chlorine rate of collecting.
Data are as follows:
Embodiment 5:
Take 240g urea, add suitable quantity of water and be configured to the urea soln that urea content is 300g/l, and add 2% magnesium chloride as protective material, after dissolving completely, be divided into two parts, a 1/3, another part 2/3, for subsequent use; Get the chlorine bleach liquor 100g that available chlorine content is 8%, add part sheet alkali wherein and make wherein containing excessive caustic soda 95g, for subsequent use;
By volume pump, the urea of 1/3 part and whole secondary sodium solutions are added mixing tank in proportion simultaneously to mix rapidly, mixing process temperature controls at 5 DEG C, be pumped in tubular heat exchange, be heated to rapidly 120 DEG C, liquid after heating directly proceeds to pressure, in the reactor that band stirs, add the urea soln of remaining 2/3 wherein simultaneously, continue to be warmed up to 160 DEG C, ammonia is not had to overflow after testing to condensation exhaust mouth, record constant temperature time is about 4h, pressure release, cool to 70 DEG C, the dilute sulphuric acid of 20% is dripped in reactor, bubble and white precipitate is had to separate out in dropping process, to pH value to 5 ~ 6, reaction terminates.Filter, washing, drying, by analysis, white depositions decomposition temperature is 248 DEG C, and be hydrazo-dicarbonamide, oven dry is weighed, and obtains hydrazo-dicarbonamide solid 104.6g, is 78.7% by the available chlorine rate of collecting
Embodiment 6:
Take 210g urea, add suitable quantity of water and be configured to the urea soln that urea content is 430g/l, and add 1% magnesium chloride as protective material, for subsequent use after dissolving completely; Get the potassium hypochlorite solution 100g that available chlorine content is 8%, add wherein part potassium hydroxide make wherein containing excessive potassium hydroxide content be 125g, for subsequent use;
By volume pump, two kinds of feed liquids are added mixing tank in proportion simultaneously to mix rapidly, mixing process temperature controls at 30 DEG C, and be pumped in tubular heat exchange, be heated to rapidly 105 DEG C, liquid after heating directly proceed to pressure, band stir reactor in, continue to be warmed up to 140 DEG C, until condensation exhaust mouth does not have ammonia to overflow after testing, record constant temperature time is about 5h, pressure release, cool to 80 DEG C, in reactor, drip hydrochloric acid, in dropping process, have bubble and white precipitate to separate out, to pH value to 6 ~ 7, reaction terminates.Filter, washing, drying, by analysis, white depositions decomposition temperature is 248 DEG C, and be hydrazo-dicarbonamide, oven dry is weighed, and obtains hydrazo-dicarbonamide solid 100.8g, is 75.8% by the available chlorine rate of collecting
The present invention, by changing urea addition, allows the sodium carbonate of by-product in hydrazine hydrate production continue and residue urea reaction.Directly hydrazo-dicarbonamide is generated under acid adding condition.Avoid the freezing of hydrazine hydrate in existing technique and remove sodium carbonate, evaporate, concentrate, more again supplement a series of complicated processes such as urea, greatly reduce power consumptions a large amount of in these processes, steam consumption.By the reduction of reaction process, decrease the loss of caustic soda, chlorine, urea, improve product yield.Above-mentioned two changes considerably reduce product cost, reclaimed the higher ammonia of added value and carbonic acid gas, hydrazo-dicarbonamide mother liquor composition becomes a salt solution of sodium chloride-containing composition simultaneously, can recycle, essentially eliminating ammonia nitrogen waste water pollution problem, is a kind of revolutionary brand-new technique.
Finally, it should be pointed out that above example is only the more representational example of the present invention.Obviously, technical scheme of the present invention is not limited to above-mentioned example, can also have many distortion, all distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, and all should think protection scope of the present invention.
Claims (6)
1. efficient low-consume cleans the technique preparing hydrazo-dicarbonamide, it is characterized in that: this technique comprises following step:
A. by the urea soln that configures and the hypochlorite solutions containing excessive highly basic, according to urea: hypochlorite: the mol ratio of highly basic is that the ratio of 3-4:1:2-2.5 adds mixing tank mixing, and mixing process controls temperature of reaction 0 DEG C-30 DEG C;
B. mixed material pumping is in tubular heat exchange, is heated rapidly to 100 DEG C-130 DEG C;
C. proceed in the reactor that with pressure, band stirs through the material of b step, be rapidly heated 130 DEG C-180 DEG C further;
D., under keeping 130 DEG C of-180 DEG C of temperature condition, pressurization constant temperature 1 ~ 8h, until condensing reflux mouth no longer produces ammonia;
E. after reaction terminates, cool to 20 DEG C-60 DEG C, acid adding in reaction solution, adjustment pH value is 4-7, and reaction terminates;
F. filter, wash, dry and can obtain hydrazo-dicarbonamide solid.
2. efficient low-consume according to claim 1 cleans the technique preparing hydrazo-dicarbonamide, it is characterized in that: described hypochlorite and highly basic are respectively clorox and sodium hydroxide, or potassium hypochlorite and potassium hydroxide, or Losantin and calcium hydroxide.
3. efficient low-consume according to claim 1 cleans the technique preparing hydrazo-dicarbonamide, it is characterized in that: regulate the organic or inorganic acid that the acid of pH value is hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid or acidity are greater than carbonic acid in described step e, pH value is preferably adjusted to 5-6.
4. efficient low-consume according to claim 1 cleans the technique preparing hydrazo-dicarbonamide, it is characterized in that: the urea in described a step drops at twice, first in a step, add urea: hypochlorite: the mol ratio of highly basic is the urea amount of 1-1.3:1:2-2.5, the urea of residue mole number adds in Step d, and the mol ratio of total urea, clorox, caustic soda is constant.
5. the efficient low-consume according to claim 1 or 4 cleans the technique preparing hydrazo-dicarbonamide, it is characterized in that: when configuring urea soln, add the magnesium chloride of the 0.5%-2% of solution quality as protective material.
6. the efficient low-consume according to claim 1 or 4 cleans the technique preparing hydrazo-dicarbonamide, it is characterized in that: in described Step d, and temperature is preferably 140 DEG C-160 DEG C.
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| CN201510096097.5A CN104761472B (en) | 2015-03-04 | 2015-03-04 | The technique that a kind of efficient low-consume cleaning prepares biruea |
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Citations (6)
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|---|---|---|---|---|
| US4482738A (en) * | 1983-08-01 | 1984-11-13 | Olin Corporation | Process for preparing semicarbazide hydrochloride |
| JP2006144077A (en) * | 2004-11-19 | 2006-06-08 | Otsuka Chemical Co Ltd | Method for producing hydrazine compound |
| CN1803899A (en) * | 2005-12-27 | 2006-07-19 | 薛式华 | Method for preparing AC blowing agent |
| CN102408359A (en) * | 2011-08-30 | 2012-04-11 | 中平能化集团开封东大化工有限公司 | Clean production method of azodicarbonamide |
| CN103755599A (en) * | 2013-12-24 | 2014-04-30 | 广西科技大学 | Preparation process of azodicarbonamide |
| CN103935971A (en) * | 2014-02-11 | 2014-07-23 | 赖中胜 | Green cycle production novel method of hydrazine hydrate, hydrazonium salts, and ADC foaming agent |
-
2015
- 2015-03-04 CN CN201510096097.5A patent/CN104761472B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482738A (en) * | 1983-08-01 | 1984-11-13 | Olin Corporation | Process for preparing semicarbazide hydrochloride |
| JP2006144077A (en) * | 2004-11-19 | 2006-06-08 | Otsuka Chemical Co Ltd | Method for producing hydrazine compound |
| CN1803899A (en) * | 2005-12-27 | 2006-07-19 | 薛式华 | Method for preparing AC blowing agent |
| CN102408359A (en) * | 2011-08-30 | 2012-04-11 | 中平能化集团开封东大化工有限公司 | Clean production method of azodicarbonamide |
| CN103755599A (en) * | 2013-12-24 | 2014-04-30 | 广西科技大学 | Preparation process of azodicarbonamide |
| CN103935971A (en) * | 2014-02-11 | 2014-07-23 | 赖中胜 | Green cycle production novel method of hydrazine hydrate, hydrazonium salts, and ADC foaming agent |
Non-Patent Citations (1)
| Title |
|---|
| 陈勇等: "联二脲清洁生产工艺初探", 《氯碱工业》, no. 6, 30 June 2007 (2007-06-30) * |
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