CN101274806A - Novel process for reclaiming waste water containing CN- and NH3 or NH4- - Google Patents
Novel process for reclaiming waste water containing CN- and NH3 or NH4- Download PDFInfo
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- CN101274806A CN101274806A CNA2007100649549A CN200710064954A CN101274806A CN 101274806 A CN101274806 A CN 101274806A CN A2007100649549 A CNA2007100649549 A CN A2007100649549A CN 200710064954 A CN200710064954 A CN 200710064954A CN 101274806 A CN101274806 A CN 101274806A
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- waste water
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- stripping
- decyanation
- acid
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Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 47
- 238000007255 decyanation reaction Methods 0.000 claims description 29
- 238000010521 absorption reaction Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 230000009615 deamination Effects 0.000 claims description 6
- 238000006481 deamination reaction Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 235000012976 tarts Nutrition 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 6
- 125000004122 cyclic group Chemical group 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 12
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- 235000002639 sodium chloride Nutrition 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- -1 Cl- Chemical class 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NCSHGROOCJHAFK-UHFFFAOYSA-N [Cl].N#CC#N Chemical compound [Cl].N#CC#N NCSHGROOCJHAFK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BNWPUUZJGBXAFM-UHFFFAOYSA-N azane oxalonitrile Chemical compound N.N#CC#N BNWPUUZJGBXAFM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method for separating HCN and NH3 for reclamation or realizing standardized discharge from wastewater solution that contains CN<-> and NH3 or NH4<+>, particularly relates to a new technique of resource cyclic utilization of high-salt cyanide and ammonium bearing wastewater, which is represented by cyanuric chloride industry, thus opening a new way of resource cyclic utilization of the high-salt cyanide and ammonium bearing wastewater, which is represented by cyanuric chloride, and providing a totally new clean production technology with simple technique, investment-saving and low operation fee and resource cyclic used feature of the integrated utilization of wastewater that contains the CN<-> and NH3 or NH4<+>.
Description
Technical field
The present invention relates to a kind of from containing CN
-And NH
3Or NH
4 +Separation and Recovery HCN and NH in the waste water solution
3The method of back reuse or qualified discharge, particularly relating to the cyanuric chloride industry is that the high salt of representative contains CN
-And NH
3Or NH
4 +The resource circulation utilization novel process of waste water.
Background technology
Through nearly 20 years development, the cyanuric chloride industry of China begins to take shape, and has formed the throughput of ten thousand tons/year of 6-8.But owing to all adopt traditional sodium cyanide method production, have that technical process is long, material consumption is high, and produce the problem of the high density chlorination sodium waste water that contains impurity such as ammonium, cyanogen, sodium formiate in a large number.Owing to contain the sodium-chlor of high density, use this waste water difficulty of biological degradation art breading bigger, simultaneously wherein contained ammonium, cyanogen and sodium formiate etc. are removed thereby other chemical physics method is also difficult. increased the complicacy and the processing cost of wastewater treatment.The precedent that the Technology and the method for such utilization of wastewater resource also do not had success at present.Therefore, the clearer production technology of exploitation cyanuric chloride and the industrial technology of waste water reclaiming recycle have great importance.
The production of cyanuric chloride is to be raw material with sodium cyanide and chlorine, and synthetic chlorine cyanogen makes cyanuric chloride through the gas phase catalysis polymerization again, and a large amount of simultaneously the generation contained the ammonia that sodium-chlor, free cyanogen and cyanogen hydrolysis produce and the waste water of sodium formiate.
Therefore, the sodium chloride-containing waste water that chlorination workshop section if can be produced is refining cheaply for electrolytic saltwater, not only can realize the resource circulation utilization, and can effectively reduce production costs to have good economy and environmental benefit.
At present, can be used for that cyanide wastewater separates and the Technology that reclaims mainly contains gas formulation, membrane separation process, solvent extration and ion exchange method.Traditional gas formulation is to utilize air or steam that cyanogen is taken out of with gas form under acidic conditions, and its technology is simple, reliability is high, but gas usage is big, and the cyanogen rate of recovery that stripping goes out is not high, and part has entered atmosphere, produces new pollution.Membrane separation process is from running condition, and film device is perfect not enough, needs to continue to be improved, and particularly on the anti-pollution ability and reproducibility of film, needs further to improve, and is beneficial to apply on a large scale.The solvent extration Treatment of Cyanide-containing Wastewater can only reclaim useful metal wherein, and prussiate is also stayed in the waste water, and this method only is applicable to the processing of the high cyanide containing wastewater that contains a large amount of metal ions.Ion exchange method exists various resins somewhat expensive at present, and operation still is in laboratory or pilot-plant test stage than problems such as complexity.
Also have the chemical process of some other Treatment of Cyanide-containing Wastewater, as alkaline oxychlorination method, this method Treatment of Cyanide-containing Wastewater is effective, equipment simple, be convenient to should realize automatization in management, the production process.Its shortcoming is: the chemical reagent consumption is big when concentration of cyanide is high, the working cost height.When hydrogen peroxide oxidation process was handled and to be contained the cyanogen gasification wastewater, speed was fast, generally can make within a short period of time the waste water CN-content after the processing reach emission request, and treating processes was very simple, and can not produce any new environmental pollution after the prussiate reaction.Shortcoming is: H
2O
2Price is more expensive, and processing cost is higher.The outstanding feature of ozone oxidation method is: do not increase other pollution substance in whole process; Technology is simple, convenient, need not chemical reagent and purchase fortune, but ozone oxidation method cost is extremely expensive, power consumption is high, ozonizer equipment complexity, maintenance difficult, bad adaptability.
The blow-off method that ammonia nitrogen removal is handled claims ammonia stripping process again, it is a kind of treatment process that bubbling air or steam are taken ammonia out of under alkaline condition, advantages such as it has that technology is simple, easy handling, investment and running cost are low, but still can not reach discharging standards for the independent stripping process of the ammonia nitrogen waste water of high density.Investment of bio-digestion method and running cost are all lower, but generally bacterium can not survive when saltiness is higher than 4000mg/l, and operation simultaneously is difficulty comparatively, and system's operation is stable inadequately, and processing back effluent quality is difficult to guarantee.The break point chlorination method is present known treatment effect the best way, almost the ammonia nitrogen in the water all can be removed, and is easy to operate, reduced investment, but very high for the treatment operating costs of high-concentration ammonia nitrogenous wastewater.Ion exchange method reduced investment, technology are simple, operation is also comparatively convenient, yet regeneration of resin is met difficulty, if with ammonia stripping regeneration then enter atmosphere and cause secondary pollution, if water absorb weak ammonia that ammonia that stripping goes out obtains generally all can not reuse, do not have export value yet.
In sum, for containing CN
-And NH
3Or NH
4 +Waste water, existing single treatment technology individual curing all exists various deficiencies, or can only the single CN that must handle in the waste water
-Or NH
3/ NH
4 +, or the chemical reagent consumption is big, the energy consumption height.The contriver explores through a large amount of tests, has invented the CN that contains that a kind of energy consumption is low, the chemical reagent consumption is few
-And NH
3Or NH
4 +The novel process for recycling of waste water can not only be with the CN in the waste water
-And NH
3Efficient recovery, and can also to make with the cyanuric chloride be that the sodium chloride brine that is produced in the production process of representative reaches electrolysis salt solution standard, characteristics economic, efficient, environmental protection that resource circulation utilization, whole waste water treatment process have embodied.
Summary of the invention
The present invention relates to a kind of from containing CN
-And NH
3Or NH
4 +Separation and Recovery HCN and NH in the waste water solution
3The method of back reuse or qualified discharge, this method may further comprise the steps:
1), the acid waste water in the decyanation tower or adjusted pH value to tart waste water bubbling air stripping go out HCN, reclaimed after absorbing with alkali lye (as sodium hydroxide solution), the waste water after the decyanation is put into deammoniation tower;
2), the waste water after the decyanation is added alkali (as sodium hydroxide, calcium oxide) and adjust waste water ph to alkaline range; The bubbling air stripping goes out NH in deammoniation tower
3, produce ammonium salt with acid (as sulfuric acid, phosphoric acid, acetic acid) absorption and reclaimed, will put into comprehensive stills for air blowing after the decyanation deamination waste water filtering disgorging matter;
3), in comprehensive stills for air blowing, add the oxygenant (as clorox, chlorine, ozone, hydrogen peroxide) of waste water weight 0.1-2% behind the stripping in the solution of residual minim cyanogen and ammonia, the oxidation after-filtration promptly gets satisfactory solution.
Fig. 1 be the present invention a kind of from waste water separation of C N
-And NH
3And the technical process of purification solution and equipment synoptic diagram.Further specify the solution of the present invention and effect below in conjunction with accompanying drawing.
Step 1) waste water is from containing CN in-And NH3Or NH4 +Waste water, Cyanuric Chloride manufacture waste water for example, this waste water can contain metal cation such as H after active metal, transition metal and the transition+、Li
+、Na
+、K
+、Ca
2+、Mg
2+、Au
+、Cu
2+、Al
3+Deng and anion such as Cl-、SO
4 2-、
SO
3 2-、PO
4 3-、S
2-、CO
3 2-、HCOO
-、CN
-Deng one or more the water of arbitrary composition Solution.
Being operating as step 1): (the pH value of waste water is less than 7 to acid waste water for the acid waste water in the decyanation tower or adjusted pH value, be preferably 2～6) pass into air stripping and go out HCN, send in the decyanation tower, pass into the stripping air, gas liquid ratio is 150～500: 1/ (m3/m
3), be preferably 200～400: 1 (m3/m
3). The air of carrying HCN secretly that stripping goes out is used after suction cyanogen tower is with alkali liquor absorption and is returned Return the decyanation tower. When Cyanide in Waste Water residual volume during less than 40mg/L, waste water is put into deammoniation tower.
Being operating as step 2): pH value of waste water in the deammoniation tower is adjusted into 10～13, is preferably 11～12; Pass into air and carry out stripping, gas liquid ratio is 500～1000: 1 (m3/m
3), be preferably 600～900: 1 (, m3/m
3). Carry NH behind the stripping secretly3Air absorb with acid after retrieval system carry out stripping, When ammonia residual volume in the waste water less than 100mg/L the time, waste water is put into comprehensive stills for air blowing.
Being operating as step 3): add a small amount of oxidant (such as clorox, chlorine, ozone, hydrogen peroxide) in comprehensive stills for air blowing, for example the oxidant of waste water weight 0.1-2% is preferably 0.5-1.5%, the CN of oxidation removal remnants-And NH3Or NH4 +With other reducing substanceses that may exist, mistake The solid matter that filters generation gets final product to get satisfactory solution.
With step 1) the cyanogen residual volume of decyanation waste water is controlled at less than 40mg/L; With with step 2) take off It is favourable to the enforcement of the inventive method that the ammonia residual volume of ammonia waste water is controlled at less than 100mg/L, this Sample can alleviate the oxidation burden in the comprehensive stills for air blowing. Yet cyanogen residual volume and ammonia residual volume be mistake a little Amount equally also is acceptable, just step 3) need to add slightly a large amount of oxidants. Oxidant Addition usually depend on CN in the waste water-And NH3Or NH4 +Residual quantity, it can be according to CN in the waste water-And NH3Or NH4 +Residual quantity adjust in right amount.
Used decyanation tower, deammoniation tower can be interior circulation type tower among the present invention, also can be packing tower, or its combination, circulation type tower in being preferably.
Proposed by the invention a kind of from the aqueous solution separation of C N
-And NH
3And the novel process of purification solution, be the CN of Separation and Recovery more than 93% under acidic conditions and under alkaline condition respectively
-And NH
3, make CN in the waste water
-Concentration is less than 40mg/L, NH
3Concentration is less than 100mg/L, the remaining CN of comprehensive then oxide treatment
-, NH
3With other reducing substanceses.With the existing CN that contains
-, NH
3Wastewater processing technology is compared, and has not only solved the blow-off method processing and has contained the cyanogen ammonia-containing water at CN
-, NH
3Energy consumption height, processing cost were higher than the problem of recovery value when concentration was low; Also solved alkaline chlorination process Treatment of Cyanide-containing Wastewater and break point chlorination Ammonia-Containing Wastewater Treatment handle the chemical reagent consumption that produces big, the problem that processing cost is high, and because the employing gas-liquid distributes, the stripping tower such as the interior ring type stripping tower of full contact carry out stripping, the vapour-liquid ratio that makes traditional blow-off method Treatment of Cyanide-containing Wastewater is by 600～900: 1 (m
3/ m
3) significantly reduce to 200～400: 1 (m
3/ m
3); The vapour-liquid ratio of stripping ammonia is by 3000～4000: 1 traditional (m
3/ m
3) reduce to 600～900: 1 (m
3/ m
3), simultaneously because the minimizing of gas usage makes the CN that stripping comes out
-And NH
3The absorption organic efficiency improve.Make whole waste water treatment process economy, effectively and reasonably.The inventive method chemical reagent consumption amount is few, facility investment and process cost is low, the entire treatment process does not have the new three wastes and produces.
Below by indefiniteness embodiment the inventive method is done and to be specified.
By flow process shown in Figure 1, the high salt that the cyanuric chloride production process is produced contains cyanogen and contains ammonium and contain sodium formiate waste water and (contain CN
-: 800mg/L, NH
4 +-N:1200mg/L, NaCl:200000mg/L, HCOONa:1200mg/L, waste water pH:8.0) is sent into the decyanation tower, and adding the hydrochloric acid adjust pH is 2.0, and feeding vapour-liquid ratio is 250: 1 (m
3/ m
3) air carry out stripping, the air of carrying HCN secretly behind the stripping returns the decyanation tower after sodium hydroxide solution absorbs HCN.800mg/L when the concentration of cyanogen was by beginning in the waste water after stripping finished drops to 20mg/L, and its stripping rate is 97.5%, and the cyanogen total amount is 7640mg in the absorption tower, and specific absorption is 97.4%.
The waste water hydro-oxidation sodium adjust pH that comes out from the decyanation tower is 11.5, sends into deammoniation tower, and feeding vapour-liquid ratio is 900: 1 (m
3/ m
3) air carry out stripping, carry NH secretly behind the stripping
3Air through sulfuric acid absorption NH
3After return deammoniation tower.1200mg/L when the concentration of ammonia was by beginning in the waste water after stripping finished drops to 60mg/L, and its stripping rate is 95%, and the ammonia total amount is 11200mg in the absorption tower, and specific absorption is 98.2%.
Waste water behind the decyanation deamination is sent into comprehensive stills for air blowing, add the chlorine bleach liquor of waste water weight 0.6%, feed pressurized air and stir, behind the catalytic oxidation 30min, transferring pH is 6～7, continues at 60 ℃ of oxide treatment 6h, the salt solution cyanogen content that filtration obtains is less than 0.01mg/L, NH
3Content is less than 1mg/L, and TOC has reached the standard of electrolysis with table salt water less than 5mg/L, can return chlor-alkali production.
Embodiment 2
By flow process shown in Figure 1, the high salt that the cyanuric chloride production process is produced contains cyanogen and contains ammonium and contain sodium formiate waste water and (contain CN
-: 800mg/L, NH
4 --N:1200mg/L, NaCl:200000mg/L, HCOONa:1200mg/L, waste water pH:8.0) is sent into the decyanation tower, and adding the hydrochloric acid adjust pH is 6.0, and feeding vapour-liquid ratio is 250: 1 (m
3/ m
3) air carry out stripping, the air of carrying HCN secretly behind the stripping returns the decyanation tower after sodium hydroxide solution absorbs HCN.800mg/L when the concentration of cyanogen was by beginning in the waste water after stripping finished drops to 40mg/L, and its stripping rate is 95%, and the cyanogen total amount is 7334mg in the absorption tower, and specific absorption is 96.5%.
The waste water hydro-oxidation sodium adjust pH that comes out from the decyanation tower is 10.5, sends into deammoniation tower, and feeding vapour-liquid ratio is 900: 1 (m
3/ m
3) air carry out stripping, carry NH secretly behind the stripping
3Air through sulfuric acid absorption NH
3After return deammoniation tower.1200mg/L when the concentration of ammonia was by beginning in the waste water after stripping finished drops to 80mg/L, and its stripping rate is 93.3%, and the ammonia total amount is 10976mg in the absorption tower, and specific absorption is 98.0%.
Waste water behind the decyanation deamination is sent into comprehensive stills for air blowing, feed salt solution cyanogen content that the ozone Oxidation Treatment after-filtration of waste water weight 0.1% obtains less than 0.01mg/L, NH
3Content is less than 1mg/L, and TOC has reached the standard of electrolysis with table salt water less than 3mg/L, returns chlor-alkali production.
Embodiment 3
By flow process shown in Figure 1, will contain CN
-: 800mg/L, CaCl
2: 20000mg/L, NH
4Cl:8000mg/L, the waste water of pH:3.0 is sent into the decyanation tower, and feeding vapour-liquid ratio is 200: 1 (m
3/ m
3) air carry out stripping, the air of carrying HCN secretly behind the stripping returns the decyanation tower after potassium hydroxide solution absorbs HCN.800mg/L when the concentration of cyanogen was by beginning in the waste water after stripping finished drops to 10mg/L, and its stripping rate is 98.8%, and the cyanogen total amount is 7750mg in the absorption tower, and specific absorption is 98.1%.
The waste water adding calcium hydroxide adjust pH that comes out from the decyanation tower is 11.5, sends into deammoniation tower, and feeding vapour-liquid ratio is 1000: 1 (m
3/ m
3) air carry out stripping, carry NH secretly behind the stripping
3Air through acetic acid absorption of N H
3After return deammoniation tower.2690mg/L when the concentration of ammonia was by beginning in the waste water after stripping finished drops to 100mg/L, and its stripping rate is 96.2%, and the ammonia total amount is 2486mg in the absorption tower, and specific absorption is 96%.
To send into comprehensive stills for air blowing behind the waste water filtering disgorging behind the decyanation deamination, promptly obtain purified calcium chloride solution after the aqueous hydrogen peroxide solution oxide treatment of adding waste water weight 1%, return to produce and use.
Embodiment 4
By flow process shown in Figure 1, will contain CN
-Be 900mg/L, NH
4 +-N:600mg/L and contain metal ions such as gold and silver, copper, zinc, lead and they and CN
-The waste water of complex compound send into the decyanation tower, adding the sulfuric acid adjust pH is 2, feeding vapour-liquid ratio is 500: 1 (m
3/ m
3) air carry out stripping, the air of carrying HCN secretly behind the stripping returns the decyanation tower after potassium hydroxide absorbs HCN.900mg/L when the concentration of cyanogen was by beginning in the waste water after stripping finished drops to 30mg/L, and its stripping rate is 96.7%, and the cyanogen total amount is 829mg in the absorption tower, and specific absorption is 95.3%.
Throw out back end hydrogenation calcium oxide or the calcium oxide adjust pH of above-mentioned decyanation waste water filtering being removed generation are 11, send into deammoniation tower, and feeding vapour-liquid ratio is 600: 1 (m
3/ m
3) air carry out stripping, carry NH secretly behind the stripping
3Air through nitric acid absorption of N H
3After return deammoniation tower.600mg/L when the concentration of ammonia was by beginning in the waste water after stripping finished drops to 40mg/L, and its stripping rate is 93.3%, and the ammonia total amount is 5499.2mg in the absorption tower, and specific absorption is 98.2%.
Send into comprehensive stills for air blowing after the waste water behind the decyanation deamination removes by filter throw out once more, add the aqueous hydrogen peroxide solution of waste water weight 1.5%, oxidation removes the throw out that deoxidation produces, and it is colourless to handle the back clarification of water, its CN
-, metal ion, NH
4 +Or NH
3, COD all reached emission standard.
Claims (8)
1. one kind from containing CN
-And NH
3Or NH
4 +Separation and Recovery HCN and NH in the waste water solution
3The method of back reuse or qualified discharge, this method may further comprise the steps:
1), the acid waste water in the decyanation tower or adjusted pH value to tart waste water bubbling air stripping go out HCN, reclaimed after absorbing with alkali lye, the waste water after the decyanation is put into deammoniation tower;
2), the waste water after the decyanation is added alkali and adjust waste water ph to alkaline range; The bubbling air stripping goes out NH in deammoniation tower
3, produce ammonium salt with the acid absorption, waste water is put into comprehensive stills for air blowing behind the deamination;
3), residual minim CN behind the stripping in comprehensive stills for air blowing
-And NH
3Or NH
4 +Solution in add oxygenant, oxidation removes by filter throw out and promptly gets satisfactory solution.
2. in accordance with the method for claim 1, it is characterized in that the alkali lye in the step 1) is aqueous sodium hydroxide solution; Step 2) alkali in is selected from sodium hydroxide and/or calcium oxide, and acid is selected from sulfuric acid, phosphoric acid or acetic acid; The oxygenant of step 3) is selected from one or more in clorox, chlorine, ozone and the hydrogen peroxide.
3. according to claim 1 or 2 described methods, the pH value that it is characterized in that waste water in the described step 1) is preferably 1～6 less than 7; Feeding stripping air vapour-liquid ratio is 150～500: 1/ (m
3/ m
3), be preferably 200～400: 1 (m
3/ m
3).
4. according to the arbitrary described method of claim 1-3, it is characterized in that described step 2) in to adjust wastewater pH be 10～13, be preferably 11～12; The bubbling air vapour-liquid ratio is 500～1000: 1 (m
3/ m
3), be preferably 600～900: 1 (m
3/ m
3).
5. according to the arbitrary described method of claim 1-4, it is characterized in that in step 2) in less than 40mg/L the time, waste water is put into deammoniation tower when cyanogen residual volume in the waste water; In step 3) when ammonia residual volume in the waste water less than 100mg/L the time, waste water is put into comprehensive stills for air blowing.
6. according to the arbitrary described method of claim 1-5, it is characterized in that adding in the described step 3) oxygenant (as clorox, chlorine, hydrogen peroxide, ozone) of waste water weight 0.1-2%, be preferably 0.5-1.5%, the CN of oxide treatment remnants
-And NH
3Or NH
4 +With other reducing substances that may exist, make it to reach reuse or emission standard.
7. according to the arbitrary described method of claim 1-6, it is characterized in that decyanation tower, deammoniation tower are interior circulation type towers, also can be packing tower, or its combination, circulation type tower in being preferably.
8. according to the arbitrary described method of claim 1-7, its described waste water is cyanuric chloride manufacture waste water.
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| ZA905224B (en) * | 1989-07-05 | 1991-04-24 | Minproc Tech | Process for reducing the cyanide content of a solution |
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