CN206666310U - A kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater - Google Patents
A kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater Download PDFInfo
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- CN206666310U CN206666310U CN201720225978.7U CN201720225978U CN206666310U CN 206666310 U CN206666310 U CN 206666310U CN 201720225978 U CN201720225978 U CN 201720225978U CN 206666310 U CN206666310 U CN 206666310U
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- phosphonomethyl
- iminodiacetic acid
- acid wastewater
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- crystallisation
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Abstract
The utility model discloses a kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater, including pretreatment, wet oxidation, stripping absorption, evaporative crystallization, crystallisation by cooling and MVR evaporated crystallization devices.The utility model uses sub-prime crystallization apparatus, ammonium sulfate, disodium hydrogen phosphate and sodium chloride crystal can be separately recovered, the purity of recovery gained crystal salt is high, and use value is high, further reduces processing cost；Water outlet after processing can carry out conventional biochemical treatment qualified discharge, and pollutants removal rate is high；Organophosphor transformation efficiency is high；Function with continuous denitrogenation, dephosphorization and desalination, and there is recycling recovery；Securely and reliably, stable, the features such as crystallization purity salt is high, operating cost is low.
Description
Technical field
The utility model belongs to water treatment field, more particularly to a kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater.
Background technology
Because herbicidal effect is good, use cost is low, glyphosate turned into that sales volume in the world is maximum at present and growth rate most
Fast pesticide species.Glyphosate synthesis route is more, and wherein iminodiacetic acid (salt) acid system (IDA methods) is due to raw material and energy resource consumption
The advantages that low, high conversion rate, has occupied leading position.During IDA method industrial production glyphosate herbicidals, intermediate double
The synthesis of sweet phosphine is essential, and this process produces a large amount of PMIDA condensation waste waters.The pH of N-(phosphonomethyl) iminodiacetic acid wastewater is 0.6~1.0,
Organic phosphorus compound containing high concentration, 2%~4% formaldehyde, organic amine, the inorganic NaCl of 18%~22% saturation etc..This is useless
Water has high concentration, high salinity, highly toxic feature, it is difficult to carries out biochemical treatment, is discharged into after water body to people, animal and ecological ring
Cause to seriously endanger in border.Meanwhile the N that contains in N-(phosphonomethyl) iminodiacetic acid wastewater, P element are also important resource, therefore at N-(phosphonomethyl) iminodiacetic acid wastewater
Reason and its nitrogen phosphor resource recovery technology are significant.
The processing equipment of N-(phosphonomethyl) iminodiacetic acid wastewater is many both at home and abroad at present, but operating cost height all be present, and crystal salt is mostly mixed
Salt, quality is low, can not recycling the defects of.
Utility model content
Purpose of utility model：For problem present in the processing of current N-(phosphonomethyl) iminodiacetic acid wastewater, the utility model provides one kind
The processing system of N-(phosphonomethyl) iminodiacetic acid wastewater simple to operate, stable, recovery gained crystallization purity salt is high, operating cost is low.
Technical scheme：A kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater described in the utility model：
Including pretreatment unit, wet oxidation device, stripping absorption device, evaporated crystallization device, equipment of crystallisation by cooling and
MVR evaporated crystallization devices；
The pretreatment unit, wet oxidation device and stripping absorption device are sequentially connected by pipeline；
The absorbing liquid outlet of the stripping absorption device is connected with evaporated crystallization device, and the stripping absorption device goes out
The mouth of a river is connected with the water inlet of equipment of crystallisation by cooling；
The delivery port of the equipment of crystallisation by cooling is connected with the water inlet of MVR evaporated crystallization devices.
The pretreatment unit includes agitating device and filter.
The pretreatment unit is provided with pH adjusting agent and adds mouth and flocculant addition mouth.
The stripping absorption device is provided with pH adjusting agent and adds mouth and absorbent addition mouth.
Going out for crystal salt is provided with the equipment of crystallisation by cooling, evaporated crystallization device and MVR evaporated crystallization devices
Mouthful, reclaim gained crystal salt for collecting.
Above-mentioned MVR evaporated crystallization devices, i.e. mechanical steam recompression evaporated crystallization device, caused by evaporator
Indirect steam, compressed through compressor, pressure, temperature rise, heat content increase, the heating chamber for being then delivered to evaporator is steamed as heating
Vapour uses, and feed liquid is maintained fluidized state, and heats steam and be then condensed into water in itself.So, the steam to be discarded originally must
Sufficient utilization have been arrived, has reclaimed latent heat, has improved the thermal efficiency again, 30 of economy equivalent to multiple-effect evaporation of raw steam are imitated,
Reduce the demand to external heat and cooling resource, reduce energy consumption, reduce pollution.
In addition, in actual use, for the normal operation of safeguards system, elevator pump can be added on pipeline as required.
Using the technique of said system processing N-(phosphonomethyl) iminodiacetic acid wastewater, comprise the following steps：
N-(phosphonomethyl) iminodiacetic acid wastewater introduces pretreatment unit by pipeline, adds pH adjusting agent liquid caustic soda, stirring and adjusting pH, adds afterwards
Flocculant filter and remove suspended substances and particulate matter；
Pretreated N-(phosphonomethyl) iminodiacetic acid wastewater introduces the oxidative degradation of wet oxidation device progress organic pollution via pipeline
Reaction；
The water outlet of wet oxidation device introduces stripping absorption device, adds pH adjusting agent liquid caustic soda, stirring and adjusting pH, Ran Houjin
Row stripping；Addition absorbent sulfuric acid is absorbed, and gained ammonium sulfate absorbing liquid introduces evaporated crystallization device, and recovery obtains ammonium sulfate
Crystal；
The water outlet of stripping desorption receiving apparatus introduces equipment of crystallisation by cooling by pipeline, and recovery obtains 12 hypophosphite monohydrate hydrogen two
Sodium crystal；
The water outlet of equipment of crystallisation by cooling introduces MVR evaporated crystallization devices by pipeline, and recovery obtains sodium chloride crystal, gained
Condensate liquid carries out subsequent biochemical processing.
Above-mentioned preprocessing process, homogeneous, pH regulations and filtration treatment are mainly carried out to waste water.
The preprocessing process, adjust pH to 7~9；The stripping absorption process, adjust pH to 11~13.
The wet oxidation reaction condition is：250~300 DEG C, 5~8MPa of reaction pressure of reaction temperature, the reaction time is anti-
Answer 0.5~2h.
By above-mentioned wet oxidation reaction, the majority of organic pollutants in waste water is oxidized degraded, and organic nitrogen is oxidized
Into ammonia nitrogen, the element such as organochlorine, phosphorus is oxidized to corresponding chlorion and phosphate anion respectively.Handled by wet oxidation,
Organophosphor transformation efficiency >=96% in waste water, COD degradation rate >=70%.
After stripping, the ammonia nitrogen in waste water is greatly lowered, and ammonia nitrogen removal frank forms sulfuric acid up to more than 90%
Ammonium absorbing liquid.
During the crystallisation by cooling, chilling temperature is -10~-5 DEG C.
By crystallisation by cooling, the disodium hydrogen phosphate dodecahydrate crystal isolated is recycled, and phosphorus organic efficiency >=
90%.
Condensate liquid biodegradability index >=0.5 after the MVR evaporative crystallizations.
Above-mentioned technique recovery gained ammonia sulfate crystal, disodium hydrogen phosphate dodecahydrate crystal and sodium chloride crystal have reached work
Industry salt standard, it can be recycled as the raw material of chemical industry.
Beneficial effect：Prior art is compared to, this technology has following advantages：
(1) harmless treatment and the recycling of N-(phosphonomethyl) iminodiacetic acid wastewater are realized, solves the ring that N-(phosphonomethyl) iminodiacetic acid wastewater is brought
Guarantor's problem, the effect that effectively prevent N-(phosphonomethyl) iminodiacetic acid wastewater conventional treatment process is unstable, is difficult to the defects of recycling；
(2) solve the problems, such as that N-(phosphonomethyl) iminodiacetic acid wastewater content of organics is high using wet oxidation device, and by organic nitrogen
Ammonia nitrogen and phosphate anion are converted into organophosphor, is provided a favorable security for the normal operation of follow-up sub-prime crystallization apparatus, favorably
In the quality for improving crystal salt, the recycling of crystal salt is realized, reduces processing cost；
(3) MVR evaporated crystallization devices are used, safety in operation is good, and investment is low with operation energy consumption, further reduction can handle
Cost；
(4) sub-prime crystallization apparatus, including evaporative crystallization, crystallisation by cooling and MVR evaporated crystallization devices are used, can be separately recovered
Ammonium sulfate, disodium hydrogen phosphate and sodium chloride crystal, the purity of crystal salt is high, and use value is high, further reduces processing cost；
(5) have the characteristics that simple to operate, stable, crystallization purity salt is high, operating cost is low, have relatively strong economical real
With property, meet national environmental protection policy requirements.
Brief description of the drawings
Fig. 1 is N-(phosphonomethyl) iminodiacetic acid wastewater processing system structural representation.
Wherein：1st, pretreatment unit；2nd, wet oxidation device；3rd, stripping absorption device；4th, evaporated crystallization device；5th, cool down
Crystallization apparatus；6th, MVR evaporated crystallization devices.A, N-(phosphonomethyl) iminodiacetic acid wastewater；B, liquid caustic soda；C, flocculant；D, pretreatment unit water outlet；E, it is wet
Formula oxidation unit water outlet；F, sulfuric acid；G, stripping absorption device water outlet；H, ammonium sulfate absorbing liquid；I, ammonia sulfate crystal；J, Shi Ershui
Close disodium hydrogen phosphate crystal；K, equipment of crystallisation by cooling water outlet；M, sodium chloride crystal；N, condensate liquid.
Embodiment
Below in conjunction with the accompanying drawings, the processing system of the utility model N-(phosphonomethyl) iminodiacetic acid wastewater is described in further detail.
Embodiment 1
A kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater as shown in Figure 1：
Including pretreatment unit 1, wet oxidation device 2, stripping absorption device 3, evaporated crystallization device 4, crystallisation by cooling dress
Put 5 and MVR evaporated crystallization devices 6；
The pretreatment unit 1, wet oxidation device 2 and stripping absorption device 3 are sequentially connected by pipeline；
The absorbing liquid outlet of the stripping absorption device 3 is connected with evaporated crystallization device 4, the stripping absorption device 3
Delivery port be connected with the water inlet of equipment of crystallisation by cooling 5；
The delivery port of the equipment of crystallisation by cooling 5 is connected with the water inlet of MVR evaporated crystallization devices 6.
The pretreatment unit 1 includes agitating device and filter.
PH adjusting agent is additionally provided with the pretreatment unit 1 and adds mouth and flocculant addition mouth；Set on stripping absorption device 3
There is pH adjusting agent to add mouth and absorbent addition mouth；Equipment of crystallisation by cooling 5, evaporated crystallization device 4 and MVR evaporated crystallization devices
Crystal salt outlet is provided with 6, gained crystal salt is reclaimed for collecting.
In addition, in actual use, for the normal operation of safeguards system, pretreatment unit 1 and wet oxidation device 2 it
Between, between wet oxidation device 2 and stripping absorption device 3, between stripping absorption device 3 and evaporated crystallization device 4, evaporative crystallization
It is provided with pipeline between device 4 and equipment of crystallisation by cooling 5, between equipment of crystallisation by cooling 5 and MVR evaporated crystallization devices 6
Elevator pump.
Embodiment 2
Using the technique of system processing N-(phosphonomethyl) iminodiacetic acid wastewater described in embodiment 1, wherein, the N-(phosphonomethyl) iminodiacetic acid wastewater of use is derived from Sichuan
Certain glyphosate pesticide manufacturing enterprise.The mean concentration of each pollutant in waste water：PH is 1.0, and suspension (SS) is 1500mg/L, is changed
It is 55000mg/L to learn oxygen demand (COD), and total phosphorus (TP) is 23000mg/L, and total nitrogen (TN) is 5000mg/L, NaCl mass concentrations
19%.
Handling process comprises the following steps：
N-(phosphonomethyl) iminodiacetic acid wastewater A enters pretreatment unit 1 by pipeline and carries out homogenization, adds liquid caustic soda B afterwards, adjusts waste water
PH is to 9, then adds flocculant C, filters off except the suspension and particulate matter in waste water, and the SS in the water outlet D of pretreatment unit 1 is reduced
For 150mg/L；
The water outlet D of pretreatment unit 1 enters wet oxidation device 2 by being provided with the pipeline of elevator pump, and waste water is in wet type
A series of chemical oxidation reaction occurs in oxidation unit 2, majority of organic pollutants is oxidized degraded, and organic nitrogen is oxidized to
The element such as ammonia nitrogen, organochlorine, phosphorus is oxidized to corresponding chlorion and phosphate anion respectively；The reaction of wet oxidation device 2
300 DEG C, reaction pressure 8MPa, reaction time 1h of temperature, the efficiency that organophosphor is converted into Phos are 98.2%, COD degradation rate
Reach 91%；The water outlet E of wet oxidation device 2 COD concentration 4950mg/L, ammonia nitrogen concentration 4600mg/L, TP concentration are
22000mg/L；
The water outlet E of wet oxidation device 2 is sent into stripping absorption device 3 by being provided with the pipeline of elevator pump, adds liquid caustic soda
B, regulation wastewater pH to 11；Absorbents of the dilute sulfuric acid F of addition 30% as stripping absorption device 3, carried using air for stripping
Gas, gas-water ratio 4000；After stripping, the ammonia nitrogen in waste water is greatly lowered, and ammonia-nitrogen desorption efficiency reaches 93%, in water outlet G
Ammonia nitrogen concentration be 322mg/L；Meanwhile the ammonium sulfate absorbing liquid H that concentration is 30% is obtained；
Water outlet G after stripping absorption device 3, mainly sodium chloride and disodium hydrogen phosphate, by the pipe for being provided with elevator pump
Road enters equipment of crystallisation by cooling 4, and waste water is cooled to -10 DEG C, and crystallization centrifuges, the 12 hypophosphite monohydrate hydrogen isolated
Two sodium crystal J are recycled, and phosphorus organic efficiency is 92%；Disodium hydrogen phosphate crystal J purity can reach industrial salt
Standard, it can be recycled as the raw material of chemical industry；
The absorbing liquid H on absorption tower, mainly 30% ammonium sulfate in stripping absorption device 3, by the pipe for being provided with elevator pump
Road enters the entrance of evaporated crystallization device 5, is evaporated concentration, crystallization, centrifuges, the ammonia sulfate crystal I isolated is carried out
Recycle；Ammonia sulfate crystal I purity can reach industrial salt standard, and recovery profit can be carried out as the raw material of chemical industry
With；
The water outlet of equipment of crystallisation by cooling 4, mainly sodium chloride, the entrance through pipeline self to MVR evaporated crystallization devices 6,
MVR evaporation and concentration, crystallization, centrifugation are carried out, the sodium chloride crystal J isolated is recycled, and condensate liquid N's is biochemical
Sex index is 0.6, carries out subsequent biochemical processing after condensate liquid N is collected again；The sodium chloride crystal M of recovery purity is reachable
To industrial salt standard, can be recycled as the raw material of chemical industry.
Embodiment 3
Using the technique of system processing N-(phosphonomethyl) iminodiacetic acid wastewater described in embodiment 1, wherein, the same embodiment of N-(phosphonomethyl) iminodiacetic acid wastewater of use
2。
With embodiment 2, difference is treatment process steps：Pretreatment stage adds liquid caustic soda B, regulation wastewater pH to 7；
250 DEG C, reaction pressure 5MPa, reaction time 0.5h of the reaction temperature of wet oxidation；Liquid caustic soda B is added during stripping absorption, regulation is useless
Water pH to 12；Cooled during crystallisation by cooling to -5 DEG C.
Result：After above-mentioned processing, the efficiency that organophosphor is converted into Phos is 96.5%；COD degradation rate reaches
To 75%；Ammonia-nitrogen desorption efficiency reaches more than 90%, and phosphorus organic efficiency is 90%；The condensate liquid of MVR evaporated crystallization devices can give birth to
Change sex index 0.5；Recovery gained ammonia sulfate crystal, disodium hydrogen phosphate dodecahydrate crystal and sodium chloride crystal have reached industrial
Salt standard.
Embodiment 4
Using the technique of system processing N-(phosphonomethyl) iminodiacetic acid wastewater described in embodiment 1, wherein, the same embodiment of N-(phosphonomethyl) iminodiacetic acid wastewater of use
2。
With embodiment 2, difference is treatment process steps：Pretreatment stage adds liquid caustic soda B, regulation wastewater pH to 8；
280 DEG C, reaction pressure 7MPa, reaction time 2h of the reaction temperature of wet oxidation；Liquid caustic soda B is added during stripping absorption, adjusts waste water
PH to 13；Cooled during crystallisation by cooling to -8 DEG C.
Result：After above-mentioned processing, the efficiency that organophosphor is converted into Phos is 97.5%；COD degradation rate reaches
To 85%；Ammonia-nitrogen desorption efficiency reaches 90%, and phosphorus organic efficiency is 91%；The condensate liquid biodegradability of MVR evaporated crystallization devices
Index 0.5；Recovery gained ammonia sulfate crystal, disodium hydrogen phosphate dodecahydrate crystal and sodium chloride crystal have reached industrial salt mark
It is accurate.
Claims (6)
- A kind of 1. processing system of N-(phosphonomethyl) iminodiacetic acid wastewater, it is characterised in that：Including pretreatment unit (1), wet oxidation device (2), stripping absorption device (3), evaporated crystallization device (4), cooling knot Brilliant device (5) and MVR evaporated crystallization devices (6)；The pretreatment unit (1), wet oxidation device (2) and stripping absorption device (3) are sequentially connected by pipeline；The absorbing liquid outlet of the stripping absorption device (3) is connected with evaporated crystallization device (4), the stripping absorption device (3) delivery port is connected with the water inlet of equipment of crystallisation by cooling (5)；The delivery port of the equipment of crystallisation by cooling (5) is connected with the water inlet of MVR evaporated crystallization devices (6).
- 2. the processing system of N-(phosphonomethyl) iminodiacetic acid wastewater according to claim 1, it is characterised in that：Pretreatment unit (1) bag Include agitating device and filter.
- 3. the processing system of N-(phosphonomethyl) iminodiacetic acid wastewater according to claim 1, it is characterised in that：On the pretreatment unit (1) Mouth is added provided with pH adjusting agent and flocculant adds mouth.
- 4. the processing system of N-(phosphonomethyl) iminodiacetic acid wastewater according to claim 1, it is characterised in that：The stripping absorption device (3) It is provided with pH adjusting agent and adds mouth and absorbent addition mouth.
- 5. the processing system of N-(phosphonomethyl) iminodiacetic acid wastewater according to claim 1, it is characterised in that：The equipment of crystallisation by cooling (5), The outlet of crystal salt is provided with evaporated crystallization device (4) and MVR evaporated crystallization devices (6), for collecting recovery gained Crystal salt.
- 6. the processing system of N-(phosphonomethyl) iminodiacetic acid wastewater according to claim 1, it is characterised in that：The pretreatment unit (1) and Between wet oxidation device (2), between wet oxidation device (2) and stripping absorption device (3), stripping absorption device (3) and steam Send out between crystallization apparatus (4), between evaporated crystallization device (4) and equipment of crystallisation by cooling (5), equipment of crystallisation by cooling (5) and MVR steamings Elevator pump is provided with pipeline between hair crystallization apparatus (6).
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| CN106746135A (en) * | 2017-03-09 | 2017-05-31 | 江苏省环境科学研究院 | The processing system and technique of a kind of N-(phosphonomethyl) iminodiacetic acid wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106746135A (en) * | 2017-03-09 | 2017-05-31 | 江苏省环境科学研究院 | The processing system and technique of a kind of N-(phosphonomethyl) iminodiacetic acid wastewater |
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