CN103896808A - Method of preparing azodiisobutyronitrile - Google Patents
Method of preparing azodiisobutyronitrile Download PDFInfo
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- CN103896808A CN103896808A CN201410144710.1A CN201410144710A CN103896808A CN 103896808 A CN103896808 A CN 103896808A CN 201410144710 A CN201410144710 A CN 201410144710A CN 103896808 A CN103896808 A CN 103896808A
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- hydrazine hydrate
- hydrazine
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- diisopropyl azodicarboxylate
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Abstract
The invention relates to a method of preparing azodiisobutyronitrile. The method comprises the following steps: a, carrying out a reaction on acetone cyanohydrin and hydrazine hydrate to generate diisobutyronitrile hydrazine; and b, introducing chlorine to diisobutyronitrile hydrazine to react to generate azodiisobutyronitrile, wherein hydrazine hydrate used in the step a is prepared by a urea method. The hydrazine hydrate is specifically prepared by the following steps: (1) introducing chlorine to a caustic soda solution to generate sodium hypochlorite; (2) adding solid urea to prepare a urea saturated solution and carrying out a reaction with sodium hypochlorite to obtain a coarse solution containing hydrazine hydrate; and (3) freezing and crystallizing the coarse solution containing hydrazine hydrate to separate sodium carbonate decahydrate so as to obtain a refined solution of hydrazine hydrate, adding a neutralizer to neutralize the pH to 2-3, removing sodium hydroxide and sodium carbonate in the solution, and then adding the refined solution of hydrazine hydrate to reversely neutralize to PH to 10-10.5. According to the method provided by the invention, the purification process of the hydrazine hydrate solution is canceled and the production procedure is simplified, so that the production cost is greatly lowered.
Description
Technical field
The invention belongs to chemical field, specifically a kind of method of preparing Diisopropyl azodicarboxylate.
Background technology
The conventional method of preparing Diisopropyl azodicarboxylate is that the acetone cyanohydrin after metering is put into synthesis reactor, add the water of 1:1, the hydrazine hydrate solution reaction being under agitation added dropwise in proportion after dilution obtains bis-isobutyronitrile hydrazine, pass into chlorine and carry out oxidizing reaction and obtain Diisopropyl azodicarboxylate, wherein hydrazine hydrate solution can be prepared by Wyler's process.
It is taking liquid caustic soda, urea, chlorine as raw material that Wyler's process is prepared hydrazine hydrate, react and just generate clorox with chlorine by liquid caustic soda, urea and catalyzer add water to be formulated as saturated solution and sodium hypochlorite reaction obtains the thick solution containing hydrazine hydrate, isolate Sodium carbonate decahydrate through freezing and crystallizing and obtain the refined soln containing hydrazine hydrate, obtain 40% hydrazine hydrate through evaporation, desalination, rectifying again, produce in 40% hydrazine hydrate process and need to consume steam 20-25 ton/ton in evaporation, desalination, rectifying, also will consume a large amount of power and waters simultaneously.Pass into chlorine and carry out oxidizing reaction and obtain the hydrochloric acid of Diisopropyl azodicarboxylate byproduct in process 8-12% at bis-isobutyronitrile hydrazine, because concentration of hydrochloric acid is low, sales difficulty, and hydrochloric acid is sold and is subject to control.In fact great majority are produced the producers of Diisopropyl azodicarboxylates and are all used in low-grade soda ash and caustic soda or lime and by-product hydrochloric acid, discharge after reaching PH=6-9, give environment.
Summary of the invention
For simplification of flowsheet, avoid evaporation, desalination, rectifying to produce the resource consumption in 40% hydrazine hydrate process, the invention provides a kind of method of preparing Diisopropyl azodicarboxylate: comprising: a. acetone cyanohydrin and hydrazine hydrate reaction generate the step of bis-isobutyronitrile hydrazine; B. bis-isobutyronitrile hydrazine passes into chlorine and carries out oxidizing reaction and generate the step of Diisopropyl azodicarboxylate and by-product hydrochloric acid waste liquid.The hydrazine hydrate using in described a step is prepared from by Wyler's process, and specific procedure is: (1) adds water 32% liquid caustic soda to be formulated as 22-26% caustic soda soln, and introduce chlorine gas to make reaction generates clorox; (2) solid urea and catalyzer are added water and be formulated as urea saturated solution, obtain the thick solution containing hydrazine hydrate with previous step gained sodium hypochlorite reaction; (3) the thick solution of hydrazine hydrate is isolated Sodium carbonate decahydrate through freezing and crystallizing and is obtained hydrazine hydrate refined soln, in hydrazine hydrate refined soln, add neutralizing agent to be neutralized to PH=2-3, eliminate sodium hydroxide and sodium carbonate in hydrazine hydrate solution, then add the anti-PH=10 of being neutralized to-10.5 of hydrazine hydrate refined soln.
The present invention has dispensed the purification process of hydrazine hydrate solution, and the hydrazine hydrate refined soln after neutralization is directly used in the flow process of producing Diisopropyl azodicarboxylate, has simplified production sequence, greatly reduces production cost.
Neutralizing agent of the present invention preferably uses the hydrochloric acid of rear operation by-product.
The by-product hydrochloric acid waste liquid of producing Diisopropyl azodicarboxylate is back among Production Flow Chart, has solved the problem of hydrochloride waste exhaust emission environment.
Embodiment
Production Flow Chart of the present invention is:
(1) preparation of the refined soln of hydrazine hydrate
32% liquid caustic soda is added water and is formulated as 22 ~ 26% caustic soda solns, and introduce chlorine gas to make reaction generates clorox; Solid urea and catalyzer are added water and be formulated as urea saturated solution, obtain the thick solution containing hydrazine hydrate with previous step gained sodium hypochlorite reaction.In the thick solution of described hydrazine hydrate, containing hydrazine hydrate, sodium-chlor, sodium hydroxide and sodium carbonate, wherein two kinds of compounds of sodium hydroxide and sodium carbonate can not be for the production of in the flow process of Diisopropyl azodicarboxylate.Because sodium hydroxide shows strong basicity, sodium carbonate shows weakly alkaline, and both existence are all on having serious impact with hydrazine hydrate and the synthetic bis-isobutyronitrile hydrazine of acetone cyanohydrin, and sodium-chlor is on synthesizing bis-isobutyronitrile hydrazine without impact.
(2) processing of the refined soln of hydrazine hydrate
By containing the thick solution of hydrazine hydrate through the freezing refined soln that obtains hydrazine hydrate after removing most of sodium carbonate (form with Sodium carbonate decahydrate crystallization is separated).Neutralizing agent adds in the refined soln of hydrazine hydrate, is neutralized to PH=2-3, and sodium hydroxide and sodium carbonate are eliminated in reaction, then adds the anti-PH=10 of being neutralized to ~ 10.5 of refined soln of hydrazine hydrate.
(3) bis-isobutyronitrile hydrazine is synthetic
Acetone cyanohydrin after metering is put into synthesis reactor, be under agitation added dropwise in proportion the hydrazine hydrate solution that second step obtains, be reacted to terminal and obtain bis-isobutyronitrile hydrazine.
(4) bis-isobutyronitrile hydrazine oxidation generates Diisopropyl azodicarboxylate
Chlorine is passed in the 3rd step and carries out oxidizing reaction in gained bis-isobutyronitrile hydrazine, obtain Diisopropyl azodicarboxylate and by-product hydrochloric acid.Wherein by-product hydrochloric acid waste liquid can be used as neutralizing agent for above-mentioned second step.And wash with water, from hydrochloric acid, reclaim the sodium-chlor of separating out.
(5) production of Diisopropyl azodicarboxylate product
Methyl alcohol or ethanol heating for dissolving for the Diisopropyl azodicarboxylate that (4) are obtained, remove by filter impurity and send crystallization in crystallization kettle, the Diisopropyl azodicarboxylate after centrifugation goes out to separate out, more drying packaging obtains Diisopropyl azodicarboxylate product.
Embodiment:
(1) 32% liquid caustic soda is added water and is formulated as 25% caustic soda soln, pass into chlorine reaction and generate clorox.Be less than 25 DEG C by chilled brine or water for cooling control temperature of reaction, obtain in chlorine bleach liquor containing available chlorine 130 ~ 135 grams per liters sodium hydroxide 150 ~ 150 grams per liters.Solid urea and catalyzer are added to the water and are formulated as urea saturated solution, urea soln obtains the thick solution containing hydrazine hydrate with DEG C reaction of clorox mixing post-heating to 110, thick solution is cooled to-10 DEG C ~-15 DEG C with chilled brine, make sodium carbonate in solution become Sodium carbonate decahydrate separates out as far as possible, go out Sodium carbonate decahydrate through centrifugation, obtain the refined soln containing hydrazine hydrate, control carbonate content 10 ~ 20 grams per liters in solution, sodium hydroxide 5 ~ 10 grams per liters.
(2) processing of the refined soln of hydrazine hydrate
The hydrochloric acid that rear operation is reclaimed under agitation adds in the refined soln of hydrazine hydrate, and hydrochloric acid reacts with the sodium carbonate in refined soln and generates carbonic acid gas, sodium-chlor and water; Hydrochloric acid reacts with the sodium hydroxide in refined soln and generates sodium-chlor and water, is first neutralized to PH=2 ~ 3, then adds the refined soln of hydrazine hydrate to be adjusted to PH=10 ~ 10.5.
(3) bis-isobutyronitrile hydrazine is synthetic
Acetone cyanohydrin after metering is put into synthesis reactor, be under agitation added dropwise in proportion the hydrazine hydrate solution that (2) obtain, be reacted to terminal and obtain bis-isobutyronitrile hydrazine.
(4) bis-isobutyronitrile hydrazine oxidation generates Diisopropyl azodicarboxylate
Chlorine is passed in the bis-isobutyronitrile hydrazine that (3) obtain, lower the temperature with chilled brine, control temperature of reaction below 20 DEG C, after being oxidized to terminal, obtain Diisopropyl azodicarboxylate, react qualified after, stop stirring and leave standstill, the Diisopropyl azodicarboxylate light specific gravity generating because of reaction swims in the upper strata of hydrochloric acid, and because of at the bottom of hydrochloric acid recycles the sodium-chlor of separating out and be deposited in still with the form of solid.The sodium-chlor of first filtered and recycled by-product, refilters and reclaims the refined soln of hydrochloric acid for the treatment of hydrazine hydrate.Diisopropyl azodicarboxylate after filtration, through washing to PH=7, send refining step.
(5) production of Diisopropyl azodicarboxylate product
Methyl alcohol or ethanol heating for dissolving for the Diisopropyl azodicarboxylate that (4) are obtained, remove by filter impurity and send crystallization in crystallization kettle, lower the temperature with chilled brine, work as crystallization, after temperature reaches 0 ~ 2 DEG C, centrifugation goes out Diisopropyl azodicarboxylate, more drying, packaging obtain Diisopropyl azodicarboxylate product.
The present invention uses the refined soln containing hydrazine hydrate of being produced by Wyler's process as raw material, directly do not use 80% hydrazine hydrate, can omit like this by the refined soln of hydrazine hydrate and obtain 80% hydrazine hydrate operation through evaporation, desalination, secondary rectifying, simplify production sequence, greatly reduce production cost.The present invention is back to the by-product hydrochloric acid waste liquid of producing Diisopropyl azodicarboxylate among Production Flow Chart, has solved the problem of hydrochloride waste exhaust emission environment.In sum, method is produced Diisopropyl azodicarboxylate thus, and raw material and energy consumption are low, and cost is low, avoids the pollution of by-product hydrochloric acid to environment.
Claims (2)
1. prepare a method for Diisopropyl azodicarboxylate, comprise that a. acetone cyanohydrin and hydrazine hydrate reaction generate the step of bis-isobutyronitrile hydrazine; B. pass into the step that chlorine carries out oxidizing reaction generation Diisopropyl azodicarboxylate and by-product hydrochloric acid waste liquid, it is characterized in that: the hydrazine hydrate using in described a step is prepared from by Wyler's process, specific procedure is: (1) adds water 32% liquid caustic soda to be formulated as 22 ~ 26% caustic soda solns, passes into chlorine reaction and generates clorox; (2) solid urea and catalyzer are added water and be formulated as urea saturated solution, obtain the thick solution containing hydrazine hydrate with previous step gained sodium hypochlorite reaction; (3) the thick solution of hydrazine hydrate is isolated Sodium carbonate decahydrate and obtains the refined soln of hydrazine hydrate through freezing and crystallizing, hydrazine hydrate refined soln adds neutralizing agent to be neutralized to PH=2 ~ 3, eliminate sodium hydroxide and sodium carbonate in hydrazine hydrate refined soln, then add the anti-PH=10 of being neutralized to ~ 10.5 of hydrazine hydrate refined soln.
2. the method for preparing Diisopropyl azodicarboxylate as claimed in claim 1, is characterized in that: described neutralizing agent refers to the by-product hydrochloric acid of rear operation oxidation gained.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484444A (en) * | 2018-05-23 | 2018-09-04 | 鲍兴亮 | Utilize the method for bromine and Hydrogen Peroxide Production azodiisobutyronitrile |
| CN109020831A (en) * | 2017-06-09 | 2018-12-18 | 辽宁双旗精细化工有限公司 | A kind of preparation method of azodiisobutyronitrile |
| CN109020832A (en) * | 2017-06-09 | 2018-12-18 | 辽宁双旗精细化工有限公司 | A kind of production method and continuous producing apparatus of hydrodiazo bis-isobutyronitrile |
| CN110922342A (en) * | 2019-11-05 | 2020-03-27 | 辽宁双旗精细化工有限公司 | Azo-bis-isobutyronitrile integrated dissolution and crystallization production device |
| CN111018742A (en) * | 2019-11-01 | 2020-04-17 | 辽宁双旗精细化工有限公司 | Device for producing azobisisobutyronitrile through continuous chlorination reaction |
| CN112851548A (en) * | 2020-12-31 | 2021-05-28 | 孙晓伟 | Method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under action of catalyst |
| CN114790153A (en) * | 2021-06-16 | 2022-07-26 | 阜阳市诗雅涤新材料科技有限公司 | Continuous synthesis method of azobisisobutyronitrile and azobisisobutyronitrile |
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| CN1745913A (en) * | 2005-10-13 | 2006-03-15 | 宜宾天原股份有限公司 | Recovering treatment of hydrated hydrazine by-product saline-alkali by urea method |
| CN1785963A (en) * | 2005-12-16 | 2006-06-14 | 上海试四赫维化工有限公司 | Preparation method of azodiisobutyronitrile |
| 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 |
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Patent Citations (3)
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| CN1745913A (en) * | 2005-10-13 | 2006-03-15 | 宜宾天原股份有限公司 | Recovering treatment of hydrated hydrazine by-product saline-alkali by urea method |
| CN1785963A (en) * | 2005-12-16 | 2006-06-14 | 上海试四赫维化工有限公司 | Preparation method of azodiisobutyronitrile |
| 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109020831A (en) * | 2017-06-09 | 2018-12-18 | 辽宁双旗精细化工有限公司 | A kind of preparation method of azodiisobutyronitrile |
| CN109020832A (en) * | 2017-06-09 | 2018-12-18 | 辽宁双旗精细化工有限公司 | A kind of production method and continuous producing apparatus of hydrodiazo bis-isobutyronitrile |
| CN108484444A (en) * | 2018-05-23 | 2018-09-04 | 鲍兴亮 | Utilize the method for bromine and Hydrogen Peroxide Production azodiisobutyronitrile |
| CN108484444B (en) * | 2018-05-23 | 2019-02-05 | 崔丽芳 | Utilize the method for bromine and Hydrogen Peroxide Production azodiisobutyronitrile |
| CN111018742A (en) * | 2019-11-01 | 2020-04-17 | 辽宁双旗精细化工有限公司 | Device for producing azobisisobutyronitrile through continuous chlorination reaction |
| CN110922342A (en) * | 2019-11-05 | 2020-03-27 | 辽宁双旗精细化工有限公司 | Azo-bis-isobutyronitrile integrated dissolution and crystallization production device |
| CN112851548A (en) * | 2020-12-31 | 2021-05-28 | 孙晓伟 | Method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under action of catalyst |
| CN114790153A (en) * | 2021-06-16 | 2022-07-26 | 阜阳市诗雅涤新材料科技有限公司 | Continuous synthesis method of azobisisobutyronitrile and azobisisobutyronitrile |
| CN114790153B (en) * | 2021-06-16 | 2024-05-10 | 阜阳市诗雅涤新材料科技有限公司 | Continuous synthesis method of azobisisobutyronitrile and azobisisobutyronitrile |
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Application publication date: 20140702 |