CN101628767A - Waste water integrated treatment method of paraquat produced by cyanamideprocess - Google Patents
Waste water integrated treatment method of paraquat produced by cyanamideprocess Download PDFInfo
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- CN101628767A CN101628767A CN200910017866A CN200910017866A CN101628767A CN 101628767 A CN101628767 A CN 101628767A CN 200910017866 A CN200910017866 A CN 200910017866A CN 200910017866 A CN200910017866 A CN 200910017866A CN 101628767 A CN101628767 A CN 101628767A
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Abstract
The invention discloses a waste water integrated treatment method of paraquat produced by cyanamideprocess, belonging to the technical field of waste water treatment. In the method, complexing agent is used for coordinately separating and recovering paraquat in waste water, a liquid membrane extraction method is used for recovering cyanide ions, double-effect distillation is used for recovering salt in the waste water, an incinerator is used for incinerating residual liquid, etc. The method has good treatment effect, high recovery rate, and can realize recycling usage of paraquat waste water resource of cyanamideprocess technique, lower pollutant in the waste water, reduce environmental pollution and lower the waste water treatment cost for paraquat manufacturing enterprises.
Description
Technical field
The present invention relates to a kind of herbicide wastewater integrated processing method, belong to technical field of waste water processing.
Background technology
Paraquat is a second largest kind in the weedicide in the world, and its demand is increasing.Domestic ammonia cyanogen method production technique obtains important breakthrough, and its technology has many good qualities, and the market competitiveness is also very strong, but the waste water handling problem that produces in its building-up process fails to be solved.The waste water that ammonia cyanogen method Paraquat production technique produces in process of production contains some paraquat product, and cyanogen radical content height, chemical oxygen demand (COD) (COD) are high, salts contg is high.Adopt general method to be difficult to remove.
Waste water distillation is earlier mainly taked in the Paraquat wastewater treatment abroad, the measure that high-concentration waste water burns, be about to the synthetic waste water that produces of Paraquat, send the thermooxidizing incinerator to, spray heavy oil, burning, organism and prussiate decompose in fire, but this method is handled about 4000～5000 yuan of the cost of waste water per ton.As seen this method investment is big, cost is high.And the useful matter in the waste water fails to reclaim, and caused the waste of resource.
By above-mentioned condition as seen, send out in the Paraquat production technique at present ammonia cyanogen, pressing for provides the method for wastewater treatment that a kind of cost is low, efficient is high, with the waste water that produces in the effective processing Paraquat production process, realize the recycling of resource, promote the sound development of Paraquat industry.
Summary of the invention
The objective of the invention is to overcome the prior art deficiency, and a kind of waste water integrated treatment method of paraquat produced by cyanamideprocess is provided, this method cost is low, and treatment effect is good.
The technical scheme that technical solution problem of the present invention is taked is:
A kind of waste water integrated treatment method of paraquat produced by cyanamideprocess may further comprise the steps:
1) recovery of Paraquat
Paraquat waste water is directly added in the reactor, stir, add complexing agent in the normal temperature and pressure downhill reaction still, separate behind the complexing agent absorption Paraquat, after press filtration, be mainly the Paraquat mother liquor in the filtrate, can be processed into 20% Paraquat aqua, sell as product.Separating back waste water enters the cyanide wastewater treatment unit and carry out step 2) recovery.
2) recovery of cyanide ion
Make water-in-oil type emulsion with tensio-active agent, additive and basic solution, under agitation add this emulsion in the cyanide wastewater, 200～300r/min stirs 8～10min, standing demix, clarification back water phase separated and organic phase, organic phase adopt high-voltage electrostatic demulsifying device breakdown of emulsion 5～10min, separate into oil phase and water, oil phase can be made newborn usefulness again, and water is recovered.
Emulsion under agitation adds in the cyanide wastewater, forms many droplets, is comprising alkaline drop (effective film 1～10 μ m, the droplet dia 0.05～0.2cm) of many diameter 1 μ m in its inside.It is long-pending that fine droplet in the waste water forms huge mass transfer surfaces, therefore, has very fast mass transfer velocity and very high selectivity.CN in the waste water
-Can be dissolved in oil phase, lean on concentration gradient to the film internal divergence in film, the NaOH reaction that runs into water in the film generates NaCN, and NaCN is an ionic compound, is insoluble to oil phase, thus can not return outer water through liquid film, thus reach CN
-Purpose in interior phase enrichment.Reaction back emulsion is through the breakdown of emulsion layering, and oil phase can be made newborn reuse again, the recyclable prussiate of water, and prussiate recycles.
3) recovery of ammonia in the waste water
Through 1), 2) handle after, the ammonia in the waste water exists with the ammonium chloride form, its content is 12wt%～17wt%.This waste water is sent into 1st effective evaporator, in micro-vacuum and 115～120 ℃ of following underpressure distillation, being concentrated into ammonium chloride content is 25wt%～28wt%, enter 2nd effect evaporator then, in vacuum tightness and 85～90 ℃ down distillations bigger than an effect evaporation, being concentrated into ammonium chloride content is 31wt%～33wt%, concentrated solution is transferred to the crystallization kettle crystallisation by cooling, isolate raffinate and ammonia chloride crystal by whizzer, raffinate reaches emission standard after burning.
The waste water integrated treatment method of described a kind of paraquat produced by cyanamideprocess, the complexing agent described in the step 1) are DSD acid (diaminostilbene disulfonic acids), and consumption is 0.2%～0.3% of a waste water weight.
Step 2) tensio-active agent described in is SPAN80 (Sorbitol Powder list olein) or E644 (polyamine) or ENJ3029 (polyamine) or blue-113 (mono butonediimides), additive is whiteruss and kerosene, basic solution is a sodium hydroxide solution, and the volume ratio of tensio-active agent and additive and basic solution is 1: 19: 20.
Described additive is the volume ratio 12: 83 of whiteruss and kerosene, and the concentration of described sodium hydroxide solution is 0.25mol/L.
Step 2) temperature is controlled at 15～35 ℃.
In the step 3) one imitate evaporation and two vacuum tightnesss of imitating evaporation be-0.05MPa～-0.1MPa between.
The invention has the beneficial effects as follows: processing effective, rate of recovery height can be realized the Paraquat utilization of wastewater resource of ammonia cyanogen method technology having reduced pollutants in waste water, has reduced the pollution to environment; Reduced the waste water treatment cost of Paraquat manufacturing enterprise simultaneously.
Description of drawings
Fig. 1 cyanide ion removal process of the present invention process flow sheet;
Fig. 2 process flow sheet of the present invention.
Embodiment
Below by embodiment the present invention is further set forth.
Embodiment 1
The recovery of Paraquat:
Untreated Paraquat waste water Paraquat content is 0.12wt%, directly add this waste water in the reactor under 25 ℃, the complexing agent DSD acid that adds Different Weight, stir, behind the complexing agent absorption Paraquat, waste water enters the cyanide wastewater treatment unit and carry out step 2) recovery, complex compound is after press filtration, be mainly the Paraquat mother liquor in the filtrate, can be processed into 20% Paraquat aqua, sell as product.The Paraquat rate of recovery sees Table 1 during the complexing agent different amounts.
Table 1
| DSD acid: waste water | ??0.001∶1 | ??0.002∶1 | ??0.0025∶1 | ??0.003∶1 | ??0.005∶1 |
| The Paraquat rate of recovery | ??92 | ??99.4 | ??99.5 | ??99.4 | ??99.2 |
Embodiment 2
The recovery of cyanide ion:
Make tensio-active agent with SPAN80, E644, ENJ3029, orchid-113 respectively; by volume mark 5%, 12% and 83% ratio are made into organic phase to get tensio-active agent, whiteruss and kerosene; place the newborn device of system; slowly add and the isopyknic NaOH solution of organic phase (0.25mol/L) after stirring; high-speed stirring 20min, make the water-in-oil emulsion of white.Get the pending water sample of 250ml cyanide ion, place separator, regulating PH with HCl is 5～7, adds the water-in-oil emulsion of the above-mentioned preparation of 20ml, and 200～300r/min stirs 8min, standing demix, and the upper strata is an organic phase, and lower floor is the aqueous solution, and clarification separates.Organic phase adopts high-voltage electrostatic demulsifying device breakdown of emulsion 5min, separates into oil phase and water.The upper strata is organic phase (can make breast again uses), and lower floor contains the NaCN aqueous solution to be the recovery product.
Tensio-active agent can influence the stability of liquid film, and it has certain influence to HCN by liquid film migration infiltration rate, and the rate of recovery of different surfaces promoting agent cyanide ion sees Table 2.
Table 2
| Tensio-active agent | ??SPAN80 | ??E644 | ??ENJ3029 | Blue-113 |
| HCN rate of recovery % | ??94.6 | ??95.2 | ??96.5 | ??99.8 |
Embodiment 3
The recovery of ammonia in the waste water:
Will be through step 1), 2) content of ammonium chloride is 14.35wt% in the waste water of Chu Liing, this waste water of 500g is added weary gas preheater earlier, one imitates the preheating of water of condensation preheater, enter 1st effective evaporator then, be warming up to 115 ℃, underpressure distillation, pressure remains on-0.06MPa, when the concentration of ammonium chloride is about 28wt% to waste water, advances one and imitate separate chamber's vapor-liquid separation, the raffinate of 1st effective evaporator is transferred to 2nd effect evaporator, temperature remains on 90 ℃, underpressure distillation, pressure be-0.075MPa, is distilled to that the concentration of ammonium chloride is about 33wt% in the waste liquid, stop distillation, waste liquid is transferred to crystallization kettle is cooled to 25 ℃ of crystallizations.Isolate raffinate and ammonia chloride crystal by whizzer, raffinate reaches emission standard after burning.The middle water that distills collects, and is back to use production.
The yield of the concentration of ammonium chloride and ammonium chloride sees Table 3 in the waste liquid.
Table 3
| One imitates distillation back raffinate amount (g) | One imitates distillation back raffinate ammonium chloride content (%) | Two imitate distillation back raffinate ammonium chloride content (%) | Crystallization Separation goes out the amount (g) of ammonium chloride |
| ??256.0 | ??28.0 | ??33.0 | ??56.3 |
Claims (5)
1, a kind of waste water integrated treatment method of paraquat produced by cyanamideprocess is characterized in that, may further comprise the steps:
1) recovery of Paraquat
Directly add Paraquat waste water in the reactor, stir, add complexing agent in the normal temperature and pressure downhill reaction still, the complexing agent that will adsorb Paraquat is separated then, after press filtration, filtrate is mainly the Paraquat mother liquor, separates waste water behind the complexing agent adsorbed Paraquat and enters the cyanide wastewater treatment unit and carry out step 2) recovery;
2) recovery of cyanide ion
Make water-in-oil type emulsion with tensio-active agent, additive and basic solution, this emulsion is under agitation added in the waste water that contains cyanide ion, 200～300r/min stirs 8～10min, standing demix, clarification back water phase separated and organic phase adopt organic phase high-voltage electrostatic demulsifying device breakdown of emulsion 5～10min then, separate into oil phase and water, oil phase is made newborn usefulness again, and water is recovered;
3) recovery of ammonia in the waste water
Will be through step 1), 2) waste water handled sends into 1st effective evaporator, in micro-vacuum and 115～120 ℃ of following underpressure distillation, being concentrated into ammonium chloride content is 25wt%～28wt%, enter 2nd effect evaporator then, in vacuum tightness and 85～90 ℃ down distillations bigger than an effect evaporation, being concentrated into ammonium chloride content is 31wt%～33wt%, concentrated solution is transferred to the crystallization kettle crystallisation by cooling, isolate raffinate and ammonia chloride crystal by whizzer, raffinate reaches emission standard after burning.
According to the waste water integrated treatment method of the described a kind of paraquat produced by cyanamideprocess of claim 1, it is characterized in that 2, the complexing agent described in the step 1) is DSD acid, consumption is 0.2%～0.3% of a waste water weight.
3, according to the waste water integrated treatment method of the described a kind of paraquat produced by cyanamideprocess of claim 1, it is characterized in that, step 2) tensio-active agent described in is SPAN80 or E644 or ENJ3029 or orchid-113, additive is whiteruss and kerosene, basic solution is a sodium hydroxide solution, and the volume ratio of tensio-active agent and additive and basic solution is 1: 19: 20.
According to the waste water integrated treatment method of the described a kind of paraquat produced by cyanamideprocess of claim 3, it is characterized in that 4, the volume ratio of described additive liquid paraffin and kerosene is 12: 83, the concentration of described sodium hydroxide solution is 0.25mol/L.
5, according to the waste water integrated treatment method of the described a kind of paraquat produced by cyanamideprocess of claim 1, it is characterized in that, in the step 3) one imitate evaporation and two vacuum tightnesss of imitating evaporation be-0.05MPa～-0.1MPa between.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626254A (en) * | 2013-11-07 | 2014-03-12 | 西安建筑科技大学 | Method for removing cyanides in cyaniding wastewater by use of emulsion liquid membrane technology |
| CN104193061A (en) * | 2014-09-02 | 2014-12-10 | 绍兴奇彩化工有限公司 | Treatment method for paraquat pesticide wastewater |
| CN109796101A (en) * | 2019-02-25 | 2019-05-24 | 安徽国星生物化学有限公司 | A kind of paraquat waste water high-efficiency, resource utilization treatment process technology |
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2009
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626254A (en) * | 2013-11-07 | 2014-03-12 | 西安建筑科技大学 | Method for removing cyanides in cyaniding wastewater by use of emulsion liquid membrane technology |
| CN103626254B (en) * | 2013-11-07 | 2015-10-21 | 西安建筑科技大学 | Liquid membrane emulsion technology is utilized to remove the method for prussiate in cyanide wastewater |
| CN104193061A (en) * | 2014-09-02 | 2014-12-10 | 绍兴奇彩化工有限公司 | Treatment method for paraquat pesticide wastewater |
| CN104193061B (en) * | 2014-09-02 | 2016-05-11 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of paraquat agricultural chemicals waste water |
| CN109796101A (en) * | 2019-02-25 | 2019-05-24 | 安徽国星生物化学有限公司 | A kind of paraquat waste water high-efficiency, resource utilization treatment process technology |
| CN109796101B (en) * | 2019-02-25 | 2022-02-22 | 安徽国星生物化学有限公司 | Highly-efficient and resource-utilization treatment process for paraquat wastewater |
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