CN103708571A - Technology for treating dilute hydrochloric acid waste liquid generated in production process of ADC (azodicarbonamide) foaming agent - Google Patents
Technology for treating dilute hydrochloric acid waste liquid generated in production process of ADC (azodicarbonamide) foaming agent Download PDFInfo
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- CN103708571A CN103708571A CN201310733122.7A CN201310733122A CN103708571A CN 103708571 A CN103708571 A CN 103708571A CN 201310733122 A CN201310733122 A CN 201310733122A CN 103708571 A CN103708571 A CN 103708571A
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Abstract
The invention provides a technology for treating dilute hydrochloric acid waste liquid generated in the production process of an ADC (azodicarbonamide) foaming agent. The technology is characterized in that a pressure-swing distillation desorption process is used for separating about 10% of dilute hydrochloric acid generated by using chlorine for oxidizing biurea in the production process of the ADC foaming agent; the dilute hydrochloric acid waste liquid enters the middle upper part of a pressure reduction tower, water is distilled off from the top of the pressure reduction tower, and hydrogen chloride gas is desorbed from the top of a pressing tower; the mass percent of the water distilled off from the top of the pressure reduction tower is greater than 99.99%, the COD (Chemical Oxygen Demand) content is less than 100mg/L, the nitrogen content is less than 100mg/L, and the water can be reused in the ADC production process; the mass percent of the hydrogen chloride desorbed from the top of the pressing tower is greater than 99.99%. The dilute hydrochloric acid waste liquid generated in the production process of the ADC foaming agent is recycled through pressure-swing distillation desorption operation, so that the treatment cost of the dilute hydrochloric acid waste liquid is reduced, and meanwhile, the damage on environments in the treatment process is also reduced.
Description
Technical field
The present invention relates to the processing method of processing and utilizing ADC whipping agent dilute hydrochloric acid waste liquid, be specifically related to adopt variable-pressure rectification desorb operating process to process the dilute hydrochloric acid waste liquid producing in ADC production process, obtain the technique of hydrogenchloride and water.
Technical background
In ADC whipping agent production process, use chlorine oxidation hydrazo-dicarbonamide to obtain Cellmic C 121 (ADC), produce the dilute hydrochloric acid waste liquid of 10wt% left and right simultaneously.Domestic ADC producer adopts in Calcium Chloride Method, absorption process, tri-chlorination iron processes, diluted acid and condensation absorption method to the processing of dilute hydrochloric acid waste water.Calcium Chloride Method can produce salt slurry contaminate environment; Absorption process foreign matter content is larger; Tri-chlorination iron processes processing power is little; In diluted acid, can reduce the throughput of ADC with condensation absorption method.
Variable-pressure rectification is a kind of widely used novel separating technology.Separation is carried out in the variation of pressure-sensitive matter utilization rectifying tower working pressure.Overcome ADC business processes dilute hydrochloric acid waste liquid and intermittently changed, polluted large, high in cost of production shortcoming.Vacuum distillation tower reboiler utilizes factory's used heat to heat, and has reduced energy consumption.
Summary of the invention
The object of the invention is to solve the processing method that ADC whipping agent enterprise dilute hydrochloric acid liquid waste disposal reclaims.The method is to adopt variable-pressure rectification desorption technique, makes dilute hydrochloric acid can isolate hydrogenchloride and water, to overcome domestic enterprise, reclaims the problem that dilute hydrochloric acid cost is higher, pollution is larger.
Content of the present invention:
A processing method of processing ADC whipping agent dilute hydrochloric acid waste liquid, is characterized in that: use variable-pressure rectification desorption process to carry out separation dilute hydrochloric acid waste liquid, concrete operations are as follows:
ADC whipping agent dilute hydrochloric acid waste liquid, obtains water through rectification under vacuum tower, and pressing and desorption tower obtains hydrogenchloride, and concrete steps are as follows:
1) dilute hydrochloric acid waste liquid enters vacuum distillation tower;
2) vacuum distillation tower reboiler uses used heat to heat, and vacuum distillation tower tower top distillates the water that purity is greater than 99.99%;
3) the hydrochloric acid azeotrope that vacuum distillation tower tower reactor distillates enters pressurizing tower desorb, and pressurizing tower tower top obtains the hydrogenchloride that purity is greater than 99.99%;
4) the hydrochloric acid circulation that pressurizing tower tower reactor distillates enters vacuum distillation tower;
5) feed liquid of circulation is carried out to certain outer row, make the COD content of the material of circulation be less than 100mg/L, ammonia-nitrogen content is less than 15mg/L.
Hydrogenchloride and water form binary azeotrope; Hydrochloric acid is in vacuum distillation tower time, and its azeotropic forms hydrogen chloride content between 21%～30%; Hydrochloric acid is in pressurizing tower time, and its azeotropic forms hydrogen chloride content between 10%～19%; Utilize the pressure change of two rectifying tower, the hydrogenchloride in hydrochloric acid is carried out separated with water.
Utilize used heat to heat the reboiler of vacuum distillation tower, reduced the energy consumption of the process that disposes waste liquid.
The working pressure of vacuum distillation tower is between 5kPa～50kPa absolute pressure, and vacuum distillation tower reflux ratio is 0.5～3:1.
The working pressure of pressurizing tower is between 200kPa～1500kPa absolute pressure, and pressurizing tower reflux ratio is 0.5～2.5:1.
The water that vacuum distillation tower tower top distillates, its COD content is between 1mg/L～100mg/L, and ammonia-nitrogen content is between 0.1mg/L～15mg/L.
Dilute hydrochloric acid waste liquid adds from the middle and upper part of vacuum distillation tower; The still liquid of vacuum distillation tower adds from the top of pressurizing tower; The still liquid of pressurizing tower adds from the middle part of vacuum distillation tower.
Comprise rectification under vacuum tower, pressing and desorption tower; Rectification under vacuum tower middle and upper part is dilute hydrochloric acid inlet pipe, rectification under vacuum tower upper end is the outlet pipe of water, rectification under vacuum tower lower end connects pressing and desorption tower middle part, and the bottom of pressing and desorption tower connects the middle and lower part of rectification under vacuum tower, and pressing and desorption tower top is hydrogenchloride outlet pipe.
The column plate of vacuum distillation tower is 5～20 layers, and the column plate of pressurizing tower is 5～30 layers.
Beneficial effect of the present invention:
The present invention is by the separated dilute hydrochloric acid of variable-pressure rectification desorption process.By the use of variable-pressure rectification, effectively processed the dilute hydrochloric acid producing in ADC enterprise production process, vacuum distillation tower tower top can obtain the water that purity is greater than 99.99%, and pressurizing tower 102 tower tops can obtain the hydrogenchloride that purity is greater than 99.99%.
Utilize used heat, with lower cost, processed the dilute hydrochloric acid waste liquid producing in ADC production process, obtained the water that can recycle and high-purity hydrogen chloride that can export trade, reduced and processed the expense of dilute hydrochloric acid waste liquid and the harm that environment is caused.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
The device of the processing method of this variable-pressure rectification desorb dilute hydrochloric acid as shown in Figure 1, comprises rectification under vacuum tower, pressing and desorption tower; Rectification under vacuum tower middle and upper part is dilute hydrochloric acid inlet pipe, rectification under vacuum tower upper end is the outlet pipe of water, rectification under vacuum tower lower end connects pressing and desorption tower middle part, and the bottom of pressing and desorption tower connects the middle and lower part of rectification under vacuum tower, and pressing and desorption tower top is hydrogenchloride outlet pipe.
The present invention uses variable-pressure rectification desorption process, the dilute hydrochloric acid waste liquid of 10% left and right that in separated ADC whipping agent production process, chlorine oxidation hydrazo-dicarbonamide produces.
The processing method that ADC whipping agent dilute hydrochloric acid waste liquid is recycled in variable-pressure rectification desorb of the present invention mainly comprises rectification under vacuum tower, pressing and desorption tower.
Described vacuum distillation tower and pressurizing tower can be tray columns, can be also packing towers.
The processing method of ADC whipping agent dilute hydrochloric acid liquid waste disposal provided by the invention utilization is to use variable-pressure rectification desorption process to carry out separation dilute hydrochloric acid waste liquid,
1) dilute hydrochloric acid waste liquid enters from vacuum distillation tower middle and upper part, and pressurization tower bottoms enters from vacuum distillation tower middle part, and vacuum distillation tower tower top obtains the water that purity is greater than 99.99%, and its COD content is less than 100mg/L, and its ammonia-nitrogen content is less than 15mg/L;
2) decompression tower bottoms enters from pressurizing tower top, the hydrogenchloride that pressurizing tower tower top solution sucking-off purity is greater than 99.99%, and pressurization tower bottoms loops back vacuum distillation tower.
A kind of processing method of processing ADC whipping agent dilute hydrochloric acid waste liquid:
The step of this processing method:
1) dilute hydrochloric acid waste liquid adds from rectification under vacuum tower middle and upper part;
2) hydrochloric acid azeotrope vacuum distillation tower tower reactor being obtained is added by the tower top of pressing and desorption tower, and pressurizing tower tower reactor hydrochloric acid azeotrope loops back vacuum distillation tower middle part;
3) will loop back pressurizing tower tower reactor hydrochloric acid azeotrope and carry out a certain amount of outer row, guarantee the normal of the interior COD content of operating system and ammonia-nitrogen content.
Vacuum distillation tower reflux ratio is at 0.5～3:1.
Pressurizing tower reflux ratio is at 0.5～2.5:1.
Vacuum distillation tower working pressure is in 5kPa～50kPa(absolute pressure) between.
Pressurizing tower working pressure is in 200kPa～1500kPa(absolute pressure) between.
Vacuum distillation tower liquid phase feeding, pressurizing tower liquid phase feeding.
Vacuum distillation tower and pressurizing tower can be tray column or packing tower.
Application Example:
Adopt Fig. 1 technical process, the working pressure of vacuum distillation tower is 20kPa(absolute pressure), the working pressure of pressurizing tower is 200kPa.
The reflux ratio of vacuum distillation tower is 0.7, and the reflux ratio of pressurizing tower is 1.1.
Result is as shown in table 1 below:
Adopt above-mentioned example, vacuum distillation tower tower top obtains the water that massfraction is greater than 99.99%, and COD content is 9.81mg/L, and ammonia-nitrogen content is 1.3mg/L; It is 99.992% hydrogenchloride that pressurizing tower tower top obtains massfraction.
Claims (9)
1. a processing method of processing ADC whipping agent dilute hydrochloric acid waste liquid, is characterized in that: use variable-pressure rectification to carry out separation dilute hydrochloric acid waste liquid, concrete operations are as follows:
ADC whipping agent dilute hydrochloric acid waste liquid, obtains water through rectification under vacuum tower, and pressing and desorption tower obtains hydrogenchloride, and concrete steps are as follows:
1) dilute hydrochloric acid waste liquid enters vacuum distillation tower;
2) vacuum distillation tower reboiler uses used heat to heat, and vacuum distillation tower tower top distillates the water that purity is greater than 99.99%;
3) the hydrochloric acid azeotrope that vacuum distillation tower tower reactor distillates enters pressing and desorption tower, and pressurizing tower tower top obtains the hydrogenchloride that purity is greater than 99.99%;
4) the hydrochloric acid circulation that pressurizing tower tower reactor distillates enters vacuum distillation tower;
5) feed liquid of circulation is carried out to certain outer row, make the COD content of the material of circulation be less than 100mg/L, ammonia-nitrogen content is less than 15mg/L.
2. a kind of processing method of processing ADC whipping agent dilute hydrochloric acid waste liquid according to claim 1, is characterized in that: hydrogenchloride and water form binary azeotrope; Hydrochloric acid is in vacuum distillation tower, and its azeotropic forms hydrogenchloride massfraction between 21%～30%; Hydrochloric acid is in pressurizing tower, and its azeotropic forms hydrogenchloride massfraction between 10%～19%; Utilize the pressure change of two rectifying tower, the hydrogenchloride in hydrochloric acid is carried out separated with water.
3. a kind of processing method of processing ADC whipping agent dilute hydrochloric acid waste liquid according to claim 1, is characterized in that: utilize used heat to heat the reboiler of vacuum distillation tower, reduced the energy consumption of the process that disposes waste liquid.
4. a kind of processing method of processing ADC whipping agent dilute hydrochloric acid waste liquid according to claim 1, is characterized in that: the working pressure of vacuum distillation tower is between 5kPa～50kPa absolute pressure, and vacuum distillation tower reflux ratio is 0.5～3:1.
5. a kind of processing method of processing ADC whipping agent dilute hydrochloric acid waste liquid according to claim 1, is characterized in that: the working pressure of pressurizing tower is between 200kPa～1500kPa absolute pressure, and pressurizing tower reflux ratio is 0.5～2.5:1.
6. the processing method of variable-pressure rectification desorb dilute hydrochloric acid according to claim 1, is characterized in that: the water that vacuum distillation tower tower top distillates, and its COD content is between 1mg/L～100mg/L, and ammonia-nitrogen content is between 0.1mg/L～15mg/L.
7. a kind of processing method of processing ADC whipping agent dilute hydrochloric acid waste liquid according to claim 1, is characterized in that: dilute hydrochloric acid waste liquid adds from the middle and upper part of vacuum distillation tower; The still liquid of vacuum distillation tower adds from the top of pressurizing tower; The middle part of the still liquid circulation vacuum distillation tower of pressurizing tower adds.
8. a kind of device of processing the processing method of ADC whipping agent dilute hydrochloric acid waste liquid according to claim 1, is characterized in that: comprise rectification under vacuum tower, pressing and desorption tower; Rectification under vacuum tower middle and upper part is dilute hydrochloric acid inlet pipe, rectification under vacuum tower upper end is the outlet pipe of water, rectification under vacuum tower lower end connects pressing and desorption tower middle part, and the bottom of pressing and desorption tower connects the middle and lower part of rectification under vacuum tower, and pressing and desorption tower top is hydrogenchloride outlet pipe.
9. a kind of device of processing the processing method of ADC whipping agent dilute hydrochloric acid waste liquid according to claim 8, is characterized in that: the column plate of vacuum distillation tower is 5～20 layers, and the column plate of pressurizing tower is 5～30 layers.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105174215A (en) * | 2015-08-26 | 2015-12-23 | 山东岩海建设资源有限公司 | Method suitable for separating and recovering hydrogen chloride from hydrochloric acid with different concentration |
| CN111422833A (en) * | 2020-03-20 | 2020-07-17 | 安徽相邦化工有限公司 | Method for preparing ultra-clean high-purity hydrochloric acid by separating hydrogen chloride from hydrochloric acid-containing mother liquor |
| CN112142008A (en) * | 2020-09-30 | 2020-12-29 | 金宏气体电子材料（淮安）有限责任公司 | Harmless treatment method of hydrochloric acid waste acid |
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| CN101289233A (en) * | 2008-05-20 | 2008-10-22 | 吴春森 | Full desorption system of hydrochloric acid |
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| CN111422833A (en) * | 2020-03-20 | 2020-07-17 | 安徽相邦化工有限公司 | Method for preparing ultra-clean high-purity hydrochloric acid by separating hydrogen chloride from hydrochloric acid-containing mother liquor |
| CN112142008A (en) * | 2020-09-30 | 2020-12-29 | 金宏气体电子材料（淮安）有限责任公司 | Harmless treatment method of hydrochloric acid waste acid |
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Application publication date: 20140409 |