CN104496100A - Recovery processing method of ammonia-nitrogen wastewater generated from nitric acid/ammonium nitrate production process - Google Patents
Recovery processing method of ammonia-nitrogen wastewater generated from nitric acid/ammonium nitrate production process Download PDFInfo
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Abstract
The invention discloses a recovery processing method of ammonia-nitrogen wastewater generated from the nitric acid/ammonium nitrate production process. Nitric acid and ammonium nitrate in wastewater are respectively recovered by a distillation technology and an ion exchange technology, and water with acid and ammonium nitrate removed returns to a production line. separated water can be used as industrial make-up water. Up-to-standard emission also can be realized. By the new two-step technology of distillation and ion exchange, ammonium nitrate acidic wastewater is processed from the source, and the present conventional process for terminal sewage treatment is optimized. The recovery processing method can be applied and popularized in the whole fertilizer enterprise. Meanwhile, a whole plant effluent segregation technology, an ammonia-removal partial nitrification technology and a combined NH4-N removal technology which are developed form a complete set of new process which can be suitable for of nitrogenous fertilizer enterprises at various scales and concentrations. Thus, it becomes possible to meet pollution control requirements of nitrogenous fertilizer enterprises on low cost, good effect and profit. The pollution control measure of source comes first and terminal treatment follows and corresponding pollution control technology are undoubtedly a comprehensive new breakthrough of a wastewater zero discharge technology.
Description
Technical field
The invention belongs to trade effluent recycling field, relate to the method for the ammonia nitrogen waste water produced in a kind of resource utilization recycling nitric acid/Ammonium Nitrate, specifically relate to a kind of rectifying and ion exchange phase combined process of adopting from waste water, reclaim nitric acid and ammonium nitrate, and make the water after process reach national grade one discharge standard discharge, also can be used as a kind of method of wastewater treatment of industrial make up water.
Technical background
Chemical fertilizer industry is the mainstay industry of China, in national economy, have consequence.But in chemical fertilizers production process, inevitably produce ammonia nitrogen waste water.Wherein, the wastewater treatment produced in traditional nitric acid, Ammonium Nitrate mainly adopts aeration tank to carry out aerobic treatment, and this plant area area is large, consumed energy is many, and processing cost is high.Waste water, after the Biochemical method of aeration tank, also has nitrogen element in water, and it mainly exists with nitrate salts, and exceeds standard in nitrate water after treatment, can cause water pollution, form potential threat to HUMAN HEALTH after discharge.Also have and adopt heterogeneous bio-reactor to process ammonia nitrogen waste water, but only adopt the aerobic treatment process of single reaction apparatus, also fail to solve the problem of azotate pollution in ammonia nitrogen waste water process water outlet.
The ammonia nitrogen waste water produced in ammonium nitrate production technique is because ammonia-nitrogen content is low, total amount large, and its process has suitable technical difficulty.Domestic ammonium nitrate production technique experienced by the development of many decades, and in industry, ammonia nitrogenous wastewater treatment technology does not obtain basic breakthrough.China publication CN02117883.6 " a kind of chemical fertilizer ammonia nitrogen waste water treatment method " discloses a kind of biochemical process, by the process of nitrification and denitrification, makes the ammonia nitrogen degradation in sewage.But this method initial cost is large, and running cost is high.Operational condition is harsh, has strict demand, as NH to influent quality
3-N index just requires at below 600mg/L, and COD index request is at below 1200mg/L, and therefore range of application is narrow.Chinese patent CN201010176871.0 discloses " a kind for the treatment of process of nitrogen-containing wastewater ", it is a kind of method that storng-acid cation exchange resin three columns in series reclaims ammonia nitrogen, the shortcoming of this technique is complex operation, stripping liquid concentration is on the low side, adsorption efficiency is poor, and is only suitable for ammonia nitrogen concentration lower (800mg/l) wastewater treatment.Also have and adopt air stripping method just to process ammonia nitrogen waste water, but when the shortcoming of this method is low temperature, stripping efficiency is low, the easy fouling of filler, and the ammonia that stripping goes out can produce secondary pollution to atmospheric environment.
Summary of the invention
Large for investment in above-mentioned technology, energy consumption is high, have the defects such as secondary pollution, the object of this invention is to provide a kind of produce from nitric acid, Ammonium Nitrate reclaim nitric acid and ammonium nitrate respectively containing in nitric acid and ammonium nitrate wastewater, make the water after process directly can return production equipment and make industrial make up water, also the method can directly externally discharged, there is good energy-conserving effect, floor space be few, cost of investment is few, treatment effect is good, the advantage of wide accommodation.
The process of the technological process of the ammonia nitrogen waste water produced in resource utilization recycling nitric acid of the present invention, ammonium nitrate production journey is, distillation technology and ion exchange technique is adopted the nitric acid in waste water and ammonium nitrate to be reclaimed respectively respectively, the water removing acid and ammonium nitrate returns production line, and the water separated can be used as industrial make up water, also qualified discharge can be realized.
The present invention is achieved through the following technical solutions:
The ammonia nitrogen waste water recovery and treatment method produced in a kind of nitric acid/Ammonium Nitrate comprises the following steps:
(1) be incorporated in rectifying tower by the high-temperature acidic waste of discharging in nitric acid production technique by pipeline, utilize the volatilization differential liberation of the nitric acid vapor in high-temperature acidic waste and water vapor to go out nitric acid, namely rectifying tower tower top discharges lower concentration nitric acid waste water solution; Discharge cone nitric acid solution at the bottom of rectifying tower, this cone nitric acid solution returns nitric acid producing system;
(2), after the lower concentration nitric acid waste water solution of discharging from rectifying tower tower top fully mixes with the nitric nitrogen waste water produced Ammonium Nitrate in tempering tank, obtain mixed solution, then allow mixed solution enter ion exchange tower and carry out purifying treatment, be specially:
Mixed solution is sent in ion exchange tower I, by the NH in h type resin group and water
4 +positively charged ion exchanges, and absorbs the NH in water
4 +positively charged ion, is swapped out the H in resin group
+ion, obtains dust technology and I grade for the treatment of solution respectively, and dust technology uses as ion exchange tower I cyclic regeneration liquid, and I grade for the treatment of solution then enters in ion exchange tower II, by the NO in hydrogen-oxygen type resin group and water
3 -negatively charged ion exchanges, and absorbs the NO in water
3 -negatively charged ion, is swapped out the hydroxide ion in resin group, removes NO in water
3 -, obtain ammonium nitrate solution and reach GB 26131 " nitric acid industry pollutant emission standard " waste water, direct discharging of waste water or recycle as industrial make up water;
(3), after gained ammonium nitrate solution in step (2) being removed metal ion and organism by adsorption filter, Ammonium Nitrate is returned.
In described step (1), high-temperature acidic waste temperature is 150-165 DEG C, concentration of nitric acid 3%-5%.
In described step (1), rectifying tower adopts tower diameter φ 1200, and material is 316,1 section of packing layer structure; The structured packing of TJC70 type selected by filler.
The lower concentration nitric acid waste water solution concentration of nitric acid 0.03-0.04% that in described step (1), rectifying tower tower top is discharged, temperature is 55-85 DEG C.
The cone nitric acid solution concentration of nitric acid of discharging at the bottom of described step (1) rectifying tower is 10%-20%, and temperature is 50-90 DEG C.
In described step (2), its nitrate of nitric nitrogen waste water is 500-1000ppm.
In described step (2), concentration of ammonium nitrate solution is 4%-6%.
Adsorption filter φ 1500 ╳ H4500 in described step (3), material Q235-A steel lining glue, interior filling cocoanut active charcoal.
The invention provides the novel process of a kind of energy comprehensive regulation nitric acid, ammonium nitrate ammonia nitrogen waste water.Adopt the novel process of rectifying-ion-exchange two step, achieve from watershed management ammonium nitrate acid waste water, the current common process for terminal sewage disposal is optimized simultaneously, can application in whole fertilizer enterprises, the full factory simultaneously also developed remove contamination dividing technology, except the short distance nitration technology of ammonia, built-up type are except NH
4-N technology, constitute can adapt to various scale, various concentration nitrogenous fertilizer enterprises adopt a whole set of novel process, make nitrogenous fertilizer enterprises pollution treatment think to spend less, effective, the requirement born interest becomes possibility.First grab source, after control the pollution treatment behave of end and corresponding pollution treatment technology, comprehensive new breakthrough of sewage zero-discharge technology beyond doubt.
Another advantage of the present invention is not only to reclaim nitric acid and ammonium nitrate, the waste water that should discharge simultaneously also reclaimed.Also large saving pollution treatment investment cost, the successful Application of this technology, mark China's Nitrogenous Fertilizer Industry sewer zero release target huge step again.
Another advantage of the present invention is that nitric acid, Process of Ammonium Nitrate Production produce the full machine breakthrough of production waste zero-discharge technology, be not only China's nitric acid, ammonium nitrate production enterprise realizes energy-conserving and environment-protective and provide technical support, and make nitrogenous fertilizer enterprises pollution treatment should spend less also to want effective requirement become possibility.New pollution treatment technology is not only effective, and investment also economizes, and compares, save one-time investment nearly ten million yuan with identical Large-scale enterprises pollution treatment investment.
Accompanying drawing explanation
Fig. 1 present invention process schematic flow sheet
In figure: 1. rectifying tower; 2. tempering tank; 3. ion exchange tower I; 4. ion exchange tower II; 5. adsorption filter.
Specific embodiments
, introduce specific embodiments of the present invention in detail by reference to the accompanying drawings below, in conjunction with comparative example, advantage of the present invention is further elaborated simultaneously.
embodiment 1
The wastewater flow rate discharged in certain nitric acid, Ammonium Nitrate is 22 tons/hour, and nitric acid content is 5%, and nitrate nitrogen content is 871ppm.
(1) as shown in Figure 1, by the high-temperature acidic waste of discharging in nitric acid production technique, (it is 165 DEG C that this high-temperature acidic waste enters its temperature of rectifying column inlet, concentration of nitric acid is 5%) be incorporated in rectifying tower 1 by pipeline, utilize the volatilization differential liberation of the nitric acid vapor in high-temperature acidic waste and water vapor to go out nitric acid, namely rectifying tower 1 tower top discharges lower concentration nitric acid waste water solution; Discharge cone nitric acid solution (also known as tower tail water) at the bottom of rectifying tower 1 tower, this cone nitric acid solution returns nitric acid producing system; As shown in table 1, lower concentration nitric acid waste water solution concentration of nitric acid 0.04%, temperature is 78 DEG C; Cone nitric acid solution concentration of nitric acid is 20%, and temperature is 83 DEG C.
(2) discharge after lower concentration nitric acid waste water solution fully mixes with the nitric nitrogen waste water produced Ammonium Nitrate in tempering tank 2 from rectifying tower 1 tower top, obtain mixed solution, mixed solution is sent in ion exchange tower I 3, by the NH in h type resin group and water
4 +positively charged ion exchanges, and absorbs the NH in water
4 +positively charged ion, is swapped out the H in resin group
+ion, obtains dust technology and I grade for the treatment of solution respectively, and dust technology uses as ion exchange tower I 3 cyclic regeneration liquid, and I grade for the treatment of solution then enters in ion exchange tower II 4, by the NO in hydrogen-oxygen type resin group and water
3 -negatively charged ion exchanges, and absorbs the NO in water
3 -negatively charged ion, is swapped out the hydroxide ion in resin group, removes NO in water
3 -, obtain ammonium nitrate solution and reach GB 26131 " nitric acid industry pollutant emission standard " waste water, direct discharging of waste water or recycle as industrial make up water;
(3), after gained ammonium nitrate solution in step (2) being removed metal ion and organism by adsorption filter, Ammonium Nitrate is returned.
Aforementioned rectifying tower 1 adopts tower diameter φ 1200, and material is 316,1 section of packing layer structure; The structured packing of TJC70 type selected by filler.
Preceding adsorption strainer 5 φ 1500 ╳ H4500, material Q235-A steel lining glue, interior filling cocoanut active charcoal.
After adopting this waste discharge of present invention process process: wherein rectifying tower reclaims nitric acid workshop section and sees the following form 1, reclaim ammonium nitrate workshop section through ion exchange tower I and II and see the following form 2, obtain the ammonium nitrate solution that concentration is 5.19%, then return ammonium nitrate production line after adsorption filter process; Waste water after purification can directly discharge or as industrial make up water.
Table 1 acid vapors distillation system operating index
。
Table 2 ion exchange method operating index
Claims (8)
1. the ammonia nitrogen waste water recovery and treatment method produced in nitric acid/Ammonium Nitrate, is characterized in that: this recovery and treatment method comprises the following steps:
(1) be incorporated in rectifying tower by the high-temperature acidic waste of discharging in nitric acid production technique by pipeline, utilize the volatilization differential liberation of the nitric acid vapor in high-temperature acidic waste and water vapor to go out nitric acid, namely rectifying tower tower top discharges lower concentration nitric acid waste water solution; Discharge cone nitric acid solution at the bottom of rectifying tower, this cone nitric acid solution returns nitric acid producing system;
(2) discharge after lower concentration nitric acid waste water solution fully mixes with the nitric nitrogen waste water produced Ammonium Nitrate in tempering tank from rectifying tower tower top, obtain mixed solution, then allow mixed solution enter ion exchange tower and carry out purifying treatment, be specially:
Mixed solution is sent in ion exchange tower I, by the NH in h type resin group and water
4 +positively charged ion exchanges, and absorbs the NH in water
4 +positively charged ion, is swapped out the H in resin group
+ion, obtains dust technology and I grade for the treatment of solution respectively, and dust technology uses as ion exchange tower I cyclic regeneration liquid, and I grade for the treatment of solution then enters in ion exchange tower II, by the NO in hydrogen-oxygen type resin group and water
3 -negatively charged ion exchanges, and absorbs the NO in water
3 -negatively charged ion, is swapped out the hydroxide ion in resin group, removes NO in water
3 -, obtain ammonium nitrate solution and reach GB 26131 " nitric acid industry pollutant emission standard " waste water, direct discharging of waste water or recycle as industrial make up water;
(3), after gained ammonium nitrate solution in step (2) being removed metal ion and organism by adsorption filter, Ammonium Nitrate is returned.
2. ammonia nitrogen waste water recovery and treatment method according to claim 1, is characterized in that: in described step (1), high-temperature acidic waste temperature is 150-165 DEG C, concentration of nitric acid 3%-5%.
3. ammonia nitrogen waste water recovery and treatment method according to claim 1, is characterized in that: in described step (1), rectifying tower adopts tower diameter φ 1200, and material is 316,1 section of packing layer structure; The structured packing of TJC70 type selected by filler.
4. ammonia nitrogen waste water recovery and treatment method according to claim 1, is characterized in that: in described step (1), rectifying tower tower top discharges lower concentration nitric acid waste water solution concentration of nitric acid 0.03-0.04%, and temperature is 55-85 DEG C.
5. ammonia nitrogen waste water recovery and treatment method according to claim 1, is characterized in that: discharging cone nitric acid solution concentration of nitric acid at the bottom of described step (1) rectifying tower is 10%-20%, and temperature is 50-90 DEG C.
6. ammonia nitrogen waste water recovery and treatment method according to claim 1, is characterized in that: in described step (2), its nitrate of nitric nitrogen waste water is 500-1000ppm.
7. ammonia nitrogen waste water recovery and treatment method according to claim 1, is characterized in that: in described step (2), concentration of ammonium nitrate solution is 4%-6%.
8. ammonia nitrogen waste water recovery and treatment method according to claim 1, is characterized in that: adsorption filter φ 1500 ╳ H4500 in described step (3), material Q235-A steel lining glue, interior filling cocoanut active charcoal.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904769A (en) * | 2017-04-28 | 2017-06-30 | 南京环保产业创新中心有限公司 | The method that the integrated absorption and desorption liquid for removing Determination of Total Nitrogen in Waste Water pollutant are applied mechanically |
| CN108698863A (en) * | 2015-12-18 | 2018-10-23 | 亚拉国际有限公司 | The method for removing removing chloride from fertilizer waste water |
| CN112573744A (en) * | 2020-11-09 | 2021-03-30 | 武汉大学 | Titanium silicon synthesis is caught up with low amine high alcohol waste water resourceful treatment system of mellow wine process |
| US11584697B2 (en) * | 2017-07-04 | 2023-02-21 | Klein Holding B.V. | Method for the production of organic fertilizer based on ammonium and/or nitrate |
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| EP0330351A1 (en) * | 1988-02-22 | 1989-08-30 | Alfred Alexander Guenkel | Processes for concentrating nitric acid |
| CN101254906A (en) * | 2008-03-17 | 2008-09-03 | 大连理工大学 | Method and device for vacuum nitric acid gas recovering during preparation of nitric acid |
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| EP0330351A1 (en) * | 1988-02-22 | 1989-08-30 | Alfred Alexander Guenkel | Processes for concentrating nitric acid |
| CN101254906A (en) * | 2008-03-17 | 2008-09-03 | 大连理工大学 | Method and device for vacuum nitric acid gas recovering during preparation of nitric acid |
| CN101891316A (en) * | 2010-07-07 | 2010-11-24 | 太原理工大学 | Process for treating nitrogen-containing wastewater by ion exchange and reclaiming ammonium nitrate |
Non-Patent Citations (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108698863A (en) * | 2015-12-18 | 2018-10-23 | 亚拉国际有限公司 | The method for removing removing chloride from fertilizer waste water |
| CN106904769A (en) * | 2017-04-28 | 2017-06-30 | 南京环保产业创新中心有限公司 | The method that the integrated absorption and desorption liquid for removing Determination of Total Nitrogen in Waste Water pollutant are applied mechanically |
| CN106904769B (en) * | 2017-04-28 | 2022-04-12 | 南京环保产业创新中心有限公司 | Method for integrated adsorption and desorption liquid application for removing total nitrogen pollutants in wastewater |
| US11584697B2 (en) * | 2017-07-04 | 2023-02-21 | Klein Holding B.V. | Method for the production of organic fertilizer based on ammonium and/or nitrate |
| AU2018297059B2 (en) * | 2017-07-04 | 2023-06-22 | Klein Holding B.V. | Method for the production of organic fertilizer based on ammonium and/or nitrate |
| CN112573744A (en) * | 2020-11-09 | 2021-03-30 | 武汉大学 | Titanium silicon synthesis is caught up with low amine high alcohol waste water resourceful treatment system of mellow wine process |
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