CN106746135A - The processing system and technique of a kind of N-(phosphonomethyl) iminodiacetic acid wastewater - Google Patents
The processing system and technique of a kind of N-(phosphonomethyl) iminodiacetic acid wastewater Download PDFInfo
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- CN106746135A CN106746135A CN201710139611.8A CN201710139611A CN106746135A CN 106746135 A CN106746135 A CN 106746135A CN 201710139611 A CN201710139611 A CN 201710139611A CN 106746135 A CN106746135 A CN 106746135A
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- Prior art keywords
- phosphonomethyl
- iminodiacetic acid
- acid wastewater
- cooling
- crystallisation
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- 239000002351 wastewater Substances 0.000 title claims abstract description 54
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 73
- 230000008025 crystallization Effects 0.000 claims abstract description 47
- 239000013078 crystal Substances 0.000 claims abstract description 38
- 238000010521 absorption reaction Methods 0.000 claims abstract description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000011780 sodium chloride Substances 0.000 claims abstract description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 8
- 230000009466 transformation Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 30
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 11
- 239000003002 pH adjusting agent Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- KVCWSJZUKMSPLM-UHFFFAOYSA-N O.O[PH2]=O Chemical compound O.O[PH2]=O KVCWSJZUKMSPLM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000013618 particulate matter Substances 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000010612 desalination reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 5
- 239000005562 Glyphosate Substances 0.000 description 4
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 4
- 229940097068 glyphosate Drugs 0.000 description 4
- -1 phosphate anion Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- 125000001477 organic nitrogen group Chemical group 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/043—Details
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses the processing system and technique of a kind of N-(phosphonomethyl) iminodiacetic acid wastewater, the system includes pretreatment, wet oxidation, stripping absorption, evaporative crystallization, crystallisation by cooling and MVR evaporated crystallization devices.The present invention uses sub-prime crystallization apparatus, can be separately recovered ammonium sulfate, disodium hydrogen phosphate and sodium chloride crystal, and the purity for reclaiming gained crystal salt is high, and use value is high, further reduces processing cost；Water outlet after being processed via present invention process 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 the effect reclaimed with resource；Safe and reliable, stable, crystallization purity salt is high, the low feature of operating cost.
Description
Technical field
The invention belongs to water treatment field, the processing system and technique of more particularly to a kind of N-(phosphonomethyl) iminodiacetic acid wastewater.
Background technology
Because herbicidal effect is good, use cost is low, and it is maximum with growth rate most that glyphosate has turned into sales volume in the world at present
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 of 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 gives up
Water has high concentration, high salinity, highly toxic feature, it is difficult to carry out biochemical treatment, enters after water body to people, animal and ecological ring
Cause serious harm 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 handling process of N-(phosphonomethyl) iminodiacetic acid wastewater is many both at home and abroad at present, but all has that operating cost is high, and crystal salt is generally mixed
Salt, quality is low, it is impossible to the defect such as recycling.
The content of the invention
Goal of the invention：For current N-(phosphonomethyl) iminodiacetic acid wastewater treatment present in problem, the invention provides one kind it is simple to operate,
Processing system that is stable, reclaiming the gained crystallization N-(phosphonomethyl) iminodiacetic acid wastewater that purity salt is high, operating cost is low, additionally provides using upper
State the technique that system processes N-(phosphonomethyl) iminodiacetic acid wastewater.
Technical scheme：A kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater of the present invention：
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 to add mouth.
The stripping absorption device is provided with pH adjusting agent and adds mouth and absorbent to add 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, using what is produced in evaporator
Indirect steam, is compressed through compressor, and pressure, temperature are raised, and heat content increases, and the heating chamber for being then delivered to evaporator is steamed as heating
Vapour is used, and feed liquid is maintained fluidized state, and is heated steam and be then condensed into water in itself.So, the steam to be discarded originally must
Sufficient utilization is arrived, latent heat has been reclaimed, the thermal efficiency has been improve again, the economy of raw steam has been imitated equivalent to the 30 of multiple-effect evaporation,
The demand to external heat and cooling resource is reduced, reducing energy consumption reduces pollution.
In addition, in actually used, for the normal operation of safeguards system, elevator pump can be as required added on pipeline.
Utilization said system of the present invention processes the technique of N-(phosphonomethyl) iminodiacetic acid wastewater, comprises the following steps：
N-(phosphonomethyl) iminodiacetic acid wastewater introduces pretreatment unit by pipeline, adds pH adjusting agent liquid caustic soda, stirring and adjusting pH to add afterwards
Flocculant filter and remove suspended substances and particulate matter；
Pretreated N-(phosphonomethyl) iminodiacetic acid wastewater introduces wet oxidation device and carries out the oxidative degradation of 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 treatment.
Above-mentioned preprocessing process, mainly carries out homogeneous, pH regulations and filtration treatment to waste water.
The preprocessing process, adjusts pH to 7~9；The stripping absorption process, adjusts pH to 11~13.
The wet oxidation reaction condition is：250~300 DEG C of reaction temperature, 5~8MPa of reaction pressure, 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.Processed 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 is up to more than 90%, while foring sulfuric acid
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.
The present invention reclaims gained ammonia sulfate crystal, disodium hydrogen phosphate dodecahydrate crystal and sodium chloride crystal and has reached industry
Salt standard is used, can be recycled as the raw material of chemical industry.
Beneficial effect：Prior art is compared to, the present invention has following advantages：
(1) N-(phosphonomethyl) iminodiacetic acid wastewater handling process of the invention, realizes harmless treatment and the resource profit of N-(phosphonomethyl) iminodiacetic acid wastewater
With, the environmental issue that N-(phosphonomethyl) iminodiacetic acid wastewater brings is solved, the effect that effectively prevent N-(phosphonomethyl) iminodiacetic acid wastewater conventional treatment process is unstable
Defect that is fixed, being difficult to recycling；
(2) PMIDA handling process of the invention, N-(phosphonomethyl) iminodiacetic acid wastewater organic matter is efficiently solved using wet oxidation device
Content problem high, and organic nitrogen and organophosphor are converted into ammonia nitrogen and phosphate anion, be follow-up sub-prime crystallization apparatus just
Often operation provides a favorable security, and is conducive to improving the quality of crystal salt, realizes the recycling of crystal salt, and reduction is processed into
This；
(3) PMIDA handling process of the invention, using MVR evaporated crystallization devices, safety in operation is good, invests and runs
Energy consumption is low, can further reduce processing cost；
(4) PMIDA handling process of the invention, using sub-prime crystallization apparatus, including evaporative crystallization, crystallisation by cooling and MVR
Evaporated crystallization device, can be separately recovered ammonium sulfate, disodium hydrogen phosphate and sodium chloride crystal, and the purity of crystal salt is high, use value
Height, further reduces processing cost；
(5) handling process of N-(phosphonomethyl) iminodiacetic acid wastewater of the invention, with it is simple to operate, stable, crystallization purity salt it is high, fortune
The low feature of row expense, with stronger economic and practical, meets national environmental protection policy requirements.
Brief description of the drawings
Fig. 1 is N-(phosphonomethyl) iminodiacetic acid wastewater processing system structural representation of the present invention.
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；It is E, 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.
Specific embodiment
Below in conjunction with the accompanying drawings, the processing system and technique of N-(phosphonomethyl) iminodiacetic acid wastewater of the present invention are 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 adds mouth and flocculant to add mouth；Set on stripping absorption device 3
There is pH adjusting agent to add mouth and absorbent to add 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 actually used, 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
The technique that N-(phosphonomethyl) iminodiacetic acid wastewater is processed using system described in embodiment 1, wherein, the N-(phosphonomethyl) iminodiacetic acid wastewater of use takes 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 is comprised the following steps：
N-(phosphonomethyl) iminodiacetic acid wastewater A carries out homogenization by pipeline into pretreatment unit 1, and liquid caustic soda B is added afterwards, adjusts waste water
PH is to 9, then adds flocculant C, suspension and particulate matter in filtering removal waste water, the SS reductions in the water outlet D of pretreatment unit 1
It is 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
There is a series of chemical oxidation reaction in oxidation unit 2, majority of organic pollutants is oxidized degraded, and organic nitrogen is oxidized to
The elements such as ammonia nitrogen, organochlorine, phosphorus are oxidized to corresponding chlorion and phosphate anion respectively；The reaction of wet oxidation device 2
300 DEG C of temperature, reaction pressure 8MPa, reaction time 1h, the efficiency that organophosphor is converted into Phos are 98.2%, COD degradation rate
Reach 91%；The COD concentration 4950mg/L of the water outlet E of wet oxidation device 2, ammonia nitrogen concentration is 4600mg/L, and TP concentration is
22000mg/L；
The water outlet E of wet oxidation device 2 sends into stripping absorption device 3 by being provided with the pipeline of elevator pump, adds liquid caustic soda
B, regulation wastewater pH to 11；Addition 30% dilute sulfuric acid F as stripping absorption device 3 absorbent, using air be stripping carry
Gas, gas-water ratio is 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, obtain the ammonium sulfate absorbing liquid H that concentration is 30%；
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, crystallizes centrifugation, the 12 hypophosphite monohydrate hydrogen isolated
Two sodium crystal J are recycled, and phosphorus organic efficiency is 92%；The purity of disodium hydrogen phosphate crystal J can reach industrial salt
Standard, 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, centrifugation, and the ammonia sulfate crystal I for isolating is carried out
Recycle；The purity of ammonia sulfate crystal I can reach industrial salt standard, can carry out reclaiming profit as the raw material of chemical industry
With；
The water outlet of equipment of crystallisation by cooling 4, mainly sodium chloride, through the entrance of pipeline self to MVR evaporated crystallization devices 6,
MVR evaporation and concentration, crystallization, centrifugation are carried out, the sodium chloride crystal J for isolating is recycled, and condensate liquid N's is biochemical
Sex index is 0.6, carries out subsequent biochemical treatment after condensate liquid N is collected again；The purity of the sodium chloride crystal M of recovery is reachable
To industrial salt standard, can be recycled as the raw material of chemical industry.
Embodiment 3
The technique that N-(phosphonomethyl) iminodiacetic acid wastewater is processed using system described in embodiment 1, wherein, the same embodiment of N-(phosphonomethyl) iminodiacetic acid wastewater of use
2。
Treatment process steps are with embodiment 2, difference：Pretreatment stage adds liquid caustic soda B, regulation wastewater pH to 7；
250 DEG C of the reaction temperature of wet oxidation, reaction pressure 5MPa, reaction time 0.5h；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 treatment, 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；Ammonia sulfate crystal, disodium hydrogen phosphate dodecahydrate crystal and sodium chloride crystal have reached industrial obtained by reclaiming
Salt standard.
Embodiment 4
The technique that N-(phosphonomethyl) iminodiacetic acid wastewater is processed using system described in embodiment 1, wherein, the same embodiment of N-(phosphonomethyl) iminodiacetic acid wastewater of use
2。
Treatment process steps are with embodiment 2, difference：Pretreatment stage adds liquid caustic soda B, regulation wastewater pH to 8；
280 DEG C of the reaction temperature of wet oxidation, reaction pressure 7MPa, reaction time 2h；Liquid caustic soda B is added during stripping absorption, waste water is adjusted
PH to 13；Cooled during crystallisation by cooling to -8 DEG C.
Result：After above-mentioned treatment, 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；Reclaim gained ammonia sulfate crystal, disodium hydrogen phosphate dodecahydrate crystal and sodium chloride crystal and reach industrial salt mark
It is accurate.
Claims (10)
1. a kind of 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)
Being provided with pH adjusting agent adds mouth and flocculant to add 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)
Being provided with pH adjusting agent adds mouth and absorbent to add mouth.
5. the technique for processing N-(phosphonomethyl) iminodiacetic acid wastewater using any system in claim 1-4, it is characterised in that including following step
Suddenly：
N-(phosphonomethyl) iminodiacetic acid wastewater introduces pretreatment unit (1) by pipeline, adds pH adjusting agent liquid caustic soda, stirring and adjusting pH to add afterwards
Flocculant, filter and remove suspended substances and particulate matter；
Pretreated N-(phosphonomethyl) iminodiacetic acid wastewater is anti-via the oxidative degradation that pipeline introducing wet oxidation device (2) carries out organic pollution
Should；
Water outlet introducing stripping absorption device (3) of wet oxidation device (2), addition pH adjusting agent liquid caustic soda, stirring and adjusting pH, then
Carry out stripping；Addition absorbent sulfuric acid is absorbed, and gained ammonium sulfate absorbing liquid introduces evaporated crystallization device (4), and recovery is obtained
Ammonia sulfate crystal；
The water outlet of stripping absorption device (3) introduces equipment of crystallisation by cooling (5) by pipeline, and recovery obtains 12 hypophosphite monohydrate hydrogen two
Sodium crystal；
The water outlet of equipment of crystallisation by cooling (5) introduces MVR evaporated crystallization devices (6) by pipeline, and recovery obtains sodium chloride crystal, institute
Obtaining condensate liquid carries out subsequent biochemical treatment.
6. technique according to claim 5, it is characterised in that the preprocessing process, adjusts pH to 7~9.
7. technique according to claim 5, it is characterised in that the stripping absorption process, adjusts pH to 11~13.
8. technique according to claim 5, it is characterised in that the wet oxidation reaction condition is：Reaction temperature 250~
300 DEG C, 5~8MPa of reaction pressure, the reaction time reacts 0.5~2h.
9. technique according to claim 5, it is characterised in that during the crystallisation by cooling, chilling temperature is -10~-5
℃。
10. technique according to claim 5, it is characterised in that organic in N-(phosphonomethyl) iminodiacetic acid wastewater after via the PROCESS FOR TREATMENT
Phosphorus transformation efficiency >=96%, COD degradation rate >=70%；Ammonia nitrogen removal frank is up to more than 90%；Phosphorus organic efficiency >=90%；MVR
Condensate liquid biodegradability index >=0.5 of evaporated crystallization device；Reclaim gained ammonia sulfate crystal, disodium hydrogen phosphate dodecahydrate brilliant
Body and sodium chloride crystal have reached industrial salt standard.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019076888A (en) * | 2017-08-28 | 2019-05-23 | 中国石油化工股▲ふん▼有限公司 | Apparatus and method for treating ammonium salt containing wastewater |
| CN110078326A (en) * | 2019-05-06 | 2019-08-02 | 姜林 | Biochemical sludge processing system and method |
| CN112225380A (en) * | 2020-10-19 | 2021-01-15 | 南通醋酸纤维有限公司 | Resource intensive phosphorus-containing wastewater treatment method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6278017B1 (en) * | 1998-08-12 | 2001-08-21 | Monsanto Company | Continuous process for the preparation of N-(phosphonomethyl)iminodiacetic acid |
| CN102115281A (en) * | 2011-01-18 | 2011-07-06 | 中国中化股份有限公司 | Method for pretreating wastewater generated in production of N-(Phosphonomethyl) iminodiaceticacid (PMIDA) |
| WO2012009860A1 (en) * | 2010-07-23 | 2012-01-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phosphonomethyl iminodiacetic acid |
| CN102583866A (en) * | 2012-03-15 | 2012-07-18 | 浙江嘉化集团股份有限公司 | Comprehensive treatment method for ammonia nitrogen wastewater generated in production of thioxophosphamide |
| CN205773845U (en) * | 2016-05-18 | 2016-12-07 | 杭州上拓环境科技有限公司 | A kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater recycling |
| CN206666310U (en) * | 2017-03-09 | 2017-11-24 | 江苏省环境科学研究院 | A kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater |
-
2017
- 2017-03-09 CN CN201710139611.8A patent/CN106746135A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6278017B1 (en) * | 1998-08-12 | 2001-08-21 | Monsanto Company | Continuous process for the preparation of N-(phosphonomethyl)iminodiacetic acid |
| WO2012009860A1 (en) * | 2010-07-23 | 2012-01-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phosphonomethyl iminodiacetic acid |
| CN102115281A (en) * | 2011-01-18 | 2011-07-06 | 中国中化股份有限公司 | Method for pretreating wastewater generated in production of N-(Phosphonomethyl) iminodiaceticacid (PMIDA) |
| CN102583866A (en) * | 2012-03-15 | 2012-07-18 | 浙江嘉化集团股份有限公司 | Comprehensive treatment method for ammonia nitrogen wastewater generated in production of thioxophosphamide |
| CN205773845U (en) * | 2016-05-18 | 2016-12-07 | 杭州上拓环境科技有限公司 | A kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater recycling |
| CN206666310U (en) * | 2017-03-09 | 2017-11-24 | 江苏省环境科学研究院 | A kind of processing system of N-(phosphonomethyl) iminodiacetic acid wastewater |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019076888A (en) * | 2017-08-28 | 2019-05-23 | 中国石油化工股▲ふん▼有限公司 | Apparatus and method for treating ammonium salt containing wastewater |
| JP2022088565A (en) * | 2017-08-28 | 2022-06-14 | 中国石油化工股▲ふん▼有限公司 | Apparatus and method for treating ammonium salt-containing wastewater |
| JP2022095769A (en) * | 2017-08-28 | 2022-06-28 | 中国石油化工股▲ふん▼有限公司 | Apparatus and method for treating wastewater containing ammonium salts |
| JP7305837B2 (en) | 2017-08-28 | 2023-07-10 | 中国石油化工股▲ふん▼有限公司 | Apparatus and method for treating wastewater containing ammonium salt |
| JP7305836B2 (en) | 2017-08-28 | 2023-07-10 | 中国石油化工股▲ふん▼有限公司 | Apparatus and method for treating wastewater containing ammonium salt |
| US11820690B2 (en) | 2017-08-28 | 2023-11-21 | China Petroleum & Chemical Corporation | Apparatus and method for treating waste water containing ammonium salts |
| CN110078326A (en) * | 2019-05-06 | 2019-08-02 | 姜林 | Biochemical sludge processing system and method |
| CN110078326B (en) * | 2019-05-06 | 2024-03-19 | 姜林 | Biochemical sludge treatment system and method |
| CN112225380A (en) * | 2020-10-19 | 2021-01-15 | 南通醋酸纤维有限公司 | Resource intensive phosphorus-containing wastewater treatment method |
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