CN103214401A - Method for lowering oxidation cost and improving quality for foamer ADC - Google Patents
Method for lowering oxidation cost and improving quality for foamer ADC Download PDFInfo
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- CN103214401A CN103214401A CN201310106530XA CN201310106530A CN103214401A CN 103214401 A CN103214401 A CN 103214401A CN 201310106530X A CN201310106530X A CN 201310106530XA CN 201310106530 A CN201310106530 A CN 201310106530A CN 103214401 A CN103214401 A CN 103214401A
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Abstract
The invention discloses a method for lowering the oxidation cost and improving the quality for the foamer ADC. The method comprises the following steps of: adopting dry or wet chlorine gas to oxidize biurea in the presence of an oxidation auxiliary; utilizing an intermittent chlorine gas feeding mode in the middle and later reaction periods; and controlling an ADC oxidation reaction end point so as to reduce peroxidating phenomena and improve the quality of the foamer ADC. The method has the beneficial effects that a practical condition that the pressure of the chlorine gas generated by an electrolytic tank is 40kPa is utilized, the chlorine gas after washing and appropriate cooling treatment can be completely and directly fed into an oxidation pot for oxidation reaction, subsequent processes such as chlorine gas dehydration and pressurization do not need to be carried out, so that the cost is greatly saved, and moreover, unstable factors influencing the production operation of the electrolytic tank are reduced. In addition, an oxidation reaction process is further subdivided, the intermittent chlorine gas feeding mode is adopted in the middle and later reaction periods, and the chlorine gas and the foamer ADC are prevented from generating side reaction to cause peroxidating to the greatest extent, so that the gas release amount of the ADC is lowered.
Description
Technical field
The present invention relates to ADC whipping agent field, be specifically related to the method that a kind of ADC of reduction whipping agent oxidation cost improves the quality.
Background technology
The universal whipping agent that ADC whipping agent (Cellmic C 121) is a consumption maximum in the foam article, purposes is the widest, because that its degradation production has is nontoxic, tasteless, nondiscoloration and advantage such as pollution-free, is widely used in plastics, the rubber items such as polyethylene, polyvinyl chloride, polystyrene, polypropylene, ABS resin and EVA.
Problems such as industrial production ADC whipping agent generally adopts chlorine oxidation at present, and the employing Sodium Bromide is a catalyzer, has oxidation cost height, and reaction control requires high, occurs peroxidation easily, and gas forming amount is lower, quality product is generally not high.
Chlorine generally will pass through a plurality of steps such as washing, lyophilize, pressurization compress and liquefy after electrolytic tank electrolysis produces, become the dry chlorine gas or the liquid chlorine of teaching high pressure, is used further to the ADC oxidation.Certainly will increase a large amount of chlorine treatment costs like this.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, and the method that provides a kind of ADC of reduction whipping agent oxidation cost to improve the quality, a kind of employing do or wet chlorine as oxygenant, the reaction middle and later periods is adopted the method for intermittently logical chlorine, the control reaction end improves ADC whipping agent method for quality.
The present invention realizes that the technical scheme that goal of the invention adopts is as follows.The method that this reduction ADC whipping agent oxidation cost improves the quality, employing is done or wet chlorine carries out oxidation to hydrazo-dicarbonamide under the condition that oxide catalyst exists, when proceeding to the middle and later periods, reaction adopts the mode of intermittently logical chlorine, the terminal point of control ADC oxidizing reaction, thereby the quality of raising ADC whipping agent.This method comprises following step:
A. with adding entry in the hydrazo-dicarbonamide, be made into the hydrazo-dicarbonamide slurry that contains hydrazo-dicarbonamide 15～40%, add the oxidation promoter Sodium Bromide simultaneously, the mass ratio of hydrazo-dicarbonamide and Sodium Bromide is 100:1;
B. the hydrazo-dicarbonamide slurry is joined in the reactor, use the blower fan exhausting, keep little negative pressure in the oxidizer, promptly-1～-10kPa.
C. pass through the refrigerant control reaction temperature between 15～50 ℃, open the chlorine valve, logical chlorine begins reaction, keeps little negative pressure in the stills for air blowing in the oxidising process;
D. sampling analysis, this reaction proceed to 70% when above, begin to carry out logical chlorine operation at intermittence; Stop logical chlorine, keep temperature in the kettle, pressure to be in response behaviour, stop for some time after, continue logical chlorine for some time, stop logical chlorine for some time again, finish until reaction.
D. after reaction finished, slip made finished product ADC whipping agent by separation, washing, drying.
As preferably, the used chlorine of oxidation is dry chlorine gas, or wet chlorine, and water ratio is zero to state of saturation.
As preferably, logical chlorine operation at described intermittence, the number of times of intermittently logical chlorine be one or many repeatedly, until thinking that reaction finishes, the logical chlorine time is 1～30min/ time, the logical chlorine speed of intermittently leading to chlorine is 0～300m
3/ h, the intermittent time is 1～40min/ time, preferably logical chlorine speed can keep the little negative pressure of reaction system.
Need to prove: reaction finishes, and adopts the caustic soda dissolution method to analyze, and the granule number of the hydrazo-dicarbonamide that contains in the 100ml reaction paste is less than 100.
Beneficial effect of the present invention is: the present invention is directed to this problem, the chlorine of producing in conjunction with electrolyzer itself just has the practical situation of 40kPa pressure, after the suitable cooling of chlorine washing, have the ability directly to enter stills for air blowing fully and carry out oxidizing reaction, unnecessaryly carrying out operations such as follow-up chlorine dewaters, pressurization, save cost greatly, simultaneously, reduced the labile factor in the electrolyzer production run.Simultaneously, innovation oxidation reaction process is further segmented in the reaction middle and later periods, adopted the mode of intermittently logical chlorine, reduces chlorine and the ADC whipping agent generation side reaction that has generated as far as possible, causes peroxidation, makes the ADC gas forming amount reduce.By this method, reaction end is easy to control, has reduced the generation of peroxidation phenomenon, has improved the quality of ADC whipping agent.
Embodiment
The present invention is further elaborated below by embodiment, and embodiment will help to understand the present invention better, but the present invention is not limited only to following embodiment.
The method that this reduction ADC whipping agent oxidation cost of the present invention improves the quality, employing is done or wet chlorine carries out oxidation to hydrazo-dicarbonamide under the condition that oxide catalyst exists, when proceeding to the middle and later periods, reaction adopts the mode of intermittently logical chlorine, the terminal point of control ADC oxidizing reaction, thereby the quality of raising ADC whipping agent.This method comprises following step:
A. with adding entry in the hydrazo-dicarbonamide, be made into the hydrazo-dicarbonamide slurry that contains hydrazo-dicarbonamide 15～40%, add the oxidation promoter Sodium Bromide simultaneously, the mass ratio of hydrazo-dicarbonamide and Sodium Bromide is 100:1;
B. the hydrazo-dicarbonamide slurry is joined in the reactor, use the blower fan exhausting, keep little negative pressure in the oxidizer, promptly-1～-10kPa.
C. pass through the refrigerant control reaction temperature between 15～50 ℃, open the chlorine valve, logical chlorine begins reaction, keeps little negative pressure in the stills for air blowing in the oxidising process;
D. sampling analysis, this reaction proceed to 70% when above, begin to carry out logical chlorine operation at intermittence; Stop logical chlorine, keep temperature in the kettle, pressure to be in response behaviour, stop for some time after, continue logical chlorine for some time, stop logical chlorine for some time again, finish until reaction.
D. after reaction finished, slip made finished product ADC whipping agent by separation, washing, drying.
By changing logical chlorine mode in the oxidising process, reduced the generation of chlorine and the side reaction of ADC whipping agent, improved the ADC quality product.Logical chlorine operation at described intermittence, the number of times of intermittently logical chlorine be one or many repeatedly, until thinking that reaction finishes, the logical chlorine time is 1～30min/ time, the logical chlorine speed of intermittently leading to chlorine is 0～300m
3/ h, the intermittent time is 1～40min/ time, preferably logical chlorine speed can keep the little negative pressure of reaction system.
Embodiment 1
Take by weighing hydrazo-dicarbonamide 150g, breaking into solid content with service water is 30% hydrazo-dicarbonamide slurry, again to wherein adding Sodium Bromide 1.5g, stirs and makes its dissolving.Slurry is poured in the glass reactor with cover of built-in coil pipe that volume is 1L, logical refrigerant in the coil pipe, the control temperature of reaction system is at 35 ℃.The tops venting port connects exhaust fan, keeps little negative pressure in the reactor.Feed chlorine by liquid chlorine cylinder gasification back to reactor bottom, chlorine feeds speed and is as the criterion to keep the little negative pressure of reactor.Finish slurries filtration, washing, oven dry post analysis gas forming amount until reaction.
Embodiment 2
Take by weighing hydrazo-dicarbonamide 150g, breaking into solid content with service water is 30% hydrazo-dicarbonamide slurry, again to wherein adding Sodium Bromide 1.5g, stirs and makes its dissolving.Slurry is poured in the glass reactor with cover of built-in coil pipe that volume is 1L, logical refrigerant in the coil pipe, the control temperature of reaction system is at 35 ℃.The tops venting port connects exhaust fan, keeps little negative pressure in the reactor.Feed chlorine by liquid chlorine cylinder gasification back to reactor bottom, chlorine feeds speed and is as the criterion to keep the little negative pressure of reactor.Reaction proceeds at 90% o'clock, stops logical chlorine, behind the 20min, continues logical chlorine 5min at interval, stops logical chlorine again, and behind the 20min, sampling analysis is reacted to terminal point, slurries filtration, washing, oven dry post analysis gas forming amount.
Embodiment 3
Take by weighing hydrazo-dicarbonamide 150g, breaking into solid content with service water is 30% hydrazo-dicarbonamide slurry, again to wherein adding Sodium Bromide 1.5g, stirs and makes its dissolving.Slurry is poured in the glass reactor with cover of built-in coil pipe that volume is 1L, logical refrigerant in the coil pipe, the control temperature of reaction system is at 35 ℃.The tops venting port connects exhaust fan, keeps little negative pressure in the reactor.Feed chlorine by liquid chlorine cylinder gasification back to reactor bottom, chlorine feeds speed and is as the criterion to keep the little negative pressure of reactor.Reaction proceeds at 80% o'clock, stops logical chlorine, behind the 20min, continues logical chlorine 10min at interval, stops logical chlorine again, behind the 20min, continues logical chlorine 5min, stops logical chlorine again, and behind the 10min, sampling analysis is reacted to terminal point, slurries filtration, washing, oven dry post analysis gas forming amount.
Embodiment 4
Take by weighing hydrazo-dicarbonamide 150g, breaking into solid content with service water is 30% hydrazo-dicarbonamide slurry, again to wherein adding Sodium Bromide 1.5g, stirs and makes its dissolving.Slurry is poured in the glass reactor with cover of built-in coil pipe that volume is 1L, logical refrigerant in the coil pipe, the control temperature of reaction system is at 35 ℃.The tops venting port connects exhaust fan, keeps little negative pressure in the reactor.Feed chlorine by liquid chlorine cylinder gasification back to reactor bottom, chlorine feeds speed and is as the criterion to keep the little negative pressure of reactor.Reaction proceeds at 70% o'clock, stops logical chlorine, at interval behind the 20min, continue logical chlorine 10min, stop logical chlorine again, behind the 20min, continue logical chlorine 5min, stop logical chlorine again, behind the 20min, continue logical chlorine 5min, stop logical chlorine again, behind the 20min, sampling analysis is reacted to terminal point, slurries filtration, washing, oven dry post analysis gas forming amount.
| Project | Gas forming amount (ml/g) |
| Embodiment 1 | 221.7 |
| Embodiment 2 | 228.4 |
| Embodiment 3 | 234.9 |
| Embodiment 4 | 239.2 |
Show that according to analytical results the ADC product that adopts method of the present invention to produce is compared with existing production technique, gas forming amount generally increases, and quality product improves a lot.
At last, should be pointed out that above example only is the more representational example of the present invention.Obviously, technical scheme of the present invention is not limited to above-mentioned example, and many distortion can also be arranged, and all distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (3)
1. one kind is reduced the method that ADC whipping agent oxidation cost improves the quality, and it is characterized in that: this method comprises following step:
A. with adding entry in the hydrazo-dicarbonamide, be made into the hydrazo-dicarbonamide slurry that contains hydrazo-dicarbonamide 15～40%, add the oxidation promoter Sodium Bromide simultaneously, the mass ratio of hydrazo-dicarbonamide and Sodium Bromide is 100:1;
B. the hydrazo-dicarbonamide slurry is joined in the reactor, use the blower fan exhausting, keep little negative pressure in the oxidizer, promptly-1～-10kPa.
C. pass through the refrigerant control reaction temperature between 15～50 ℃, open the chlorine valve, logical chlorine begins reaction, keeps little negative pressure in the stills for air blowing in the oxidising process;
D. sampling analysis, this reaction proceed to 70% when above, begin to carry out logical chlorine operation at intermittence; Stop logical chlorine, keep temperature in the kettle, pressure to be in response behaviour, stop for some time after, continue logical chlorine for some time, stop logical chlorine for some time again, finish until reaction.
D. after reaction finished, slip made finished product ADC whipping agent by separation, washing, drying.
2. kind according to claim 1 reduces the method that ADC whipping agent oxidation cost improves the quality, and it is characterized in that: the used chlorine of oxidation is dry chlorine gas, or wet chlorine, and water ratio is zero to state of saturation.
3. kind according to claim 1 reduces the method that ADC whipping agent oxidation cost improves the quality, it is characterized in that: logical chlorine operation at described intermittence, intermittently the number of times of logical chlorine be one or many repeatedly, until thinking that reaction finishes, the logical chlorine time is 1～30min/ time, and the logical chlorine speed of intermittently logical chlorine is 0～300m
3/ h, the intermittent time is 1～40min/ time.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310106530XA CN103214401A (en) | 2013-03-28 | 2013-03-28 | Method for lowering oxidation cost and improving quality for foamer ADC |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310106530XA CN103214401A (en) | 2013-03-28 | 2013-03-28 | Method for lowering oxidation cost and improving quality for foamer ADC |
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| CN103214401A true CN103214401A (en) | 2013-07-24 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB959761A (en) * | 1962-05-31 | 1964-06-03 | Us Rubber Co | Manufacture of azodicarbonamide |
| US3528962A (en) * | 1966-07-29 | 1970-09-15 | Bayer Ag | Process for the production of azodicarbonamide |
| CN101219974A (en) * | 2008-01-22 | 2008-07-16 | 浙江海虹控股集团有限公司 | Method for recovery utilization of mother solution hydrochloric acid for ADC foaming agent production |
| CN102675158A (en) * | 2012-05-10 | 2012-09-19 | 杭州海虹精细化工有限公司 | Method for producing ADC foaming agent by using chlorine gas-oxidized HDCA (biurea) in saturated hydrochloric acid solution |
-
2013
- 2013-03-28 CN CN201310106530XA patent/CN103214401A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB959761A (en) * | 1962-05-31 | 1964-06-03 | Us Rubber Co | Manufacture of azodicarbonamide |
| US3528962A (en) * | 1966-07-29 | 1970-09-15 | Bayer Ag | Process for the production of azodicarbonamide |
| CN101219974A (en) * | 2008-01-22 | 2008-07-16 | 浙江海虹控股集团有限公司 | Method for recovery utilization of mother solution hydrochloric acid for ADC foaming agent production |
| CN102675158A (en) * | 2012-05-10 | 2012-09-19 | 杭州海虹精细化工有限公司 | Method for producing ADC foaming agent by using chlorine gas-oxidized HDCA (biurea) in saturated hydrochloric acid solution |
Non-Patent Citations (4)
| Title |
|---|
| 《江苏化工》 19940228 宫泉渌，狄伯秋 氯气法生产AC发泡剂工艺的改进--氯气添加尿素氧化法 第22-23页 1-3 第22卷, 第2期 * |
| 安先义: "ADC发泡剂氯化釜爆炸事故分析", 《氯碱工业》 * |
| 宫泉渌，狄伯秋: "氯气法生产AC发泡剂工艺的改进——氯气添加尿素氧化法", 《江苏化工》 * |
| 澹台姝娴: "ADC发泡剂生产工艺的改进", 《氯碱工业》 * |
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Application publication date: 20130724 |