CN105836930A - Water-film integrated processing process of high-salt-content wastewater generated by hydrazine hydrate production using ketazine method - Google Patents
Water-film integrated processing process of high-salt-content wastewater generated by hydrazine hydrate production using ketazine method Download PDFInfo
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- CN105836930A CN105836930A CN201610381572.8A CN201610381572A CN105836930A CN 105836930 A CN105836930 A CN 105836930A CN 201610381572 A CN201610381572 A CN 201610381572A CN 105836930 A CN105836930 A CN 105836930A
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- 238000000034 method Methods 0.000 title claims abstract description 71
- 239000002351 wastewater Substances 0.000 title claims abstract description 37
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 title claims abstract description 22
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001471 micro-filtration Methods 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 238000001728 nano-filtration Methods 0.000 claims abstract description 18
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000007670 refining Methods 0.000 claims abstract description 4
- 239000005416 organic matter Substances 0.000 claims abstract 2
- 239000012528 membrane Substances 0.000 claims description 36
- 238000006385 ozonation reaction Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000012466 permeate Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 abstract description 4
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 5
- 235000013877 carbamide Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- -1 has Raschig process Chemical compound 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- DKHKTHAFPUYTLR-UHFFFAOYSA-N azane;hydrazine;hydrate Chemical compound N.O.NN DKHKTHAFPUYTLR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- 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
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to water-film integrated processing process of high-salt-content wastewater generated by hydrazine hydrate production using a ketazine method. The water-film integrated processing process includes: performing microfiltration on the high-salt-content wastewater generated by the hydrazine hydrate production using the ketazine method after absorption, allowing the clean water after the microfiltration to enter a nano-filtration process, allowing the penetrating fluid after the nano-filtration to enter an ozone catalytic oxidization system, allowing thick water to circulate and enter absorption treatment, conveying the wastewater after the ozone catalytic oxidization to air stripping treatment, and then removing the salt water and refining. The water-film integrated processing process has the advantages the water-film integrated processing technology is used, organic matter and inorganic salt are separated effectively, and the process is advanced, simple to operate, stable and reliable in effect, and the like.
Description
Technical field
The invention belongs to environment-protective water process field, relate to the high saliferous of a kind of preparation of hydrazine hydrate by use of ketazine
Wastewater membrane method integrated treatment process.
Background technology
Hydrazine hydrate, also known as hydrazine hydrate, is a kind of important fine chemical material.Hydrazine hydrate can be used
In synthesis multiple foaming agent, cleaning treatment agent, it is possible to as medicine, herbicide, rubber chemicals,
The fields such as rocket fuel.The synthetic method of hydrazine hydrate mainly has Raschig process, urea method, ketazine process
With hydrogen peroxide method etc..Raschig process is with ammonia for nitrogen source, with hypochlorite oxidation ammonia hydrazine hydrate,
Owing to this method need to use excess of ammonia, while retracting device need to be set up, also produce substantial amounts of sodium chloride
With salt such as ammonium chloride.The environmental pollution ratio that Raschig process produces is more serious, and investment is big, and product yield is low,
So method is eliminated the most substantially.Urea method makees oxidant with sodium hypochlorite, prepares with carbamide for nitrogen source
Hydrazine hydrate.The advantages such as it is low that urea method has investment, and equipment is simple, but due to the raw material used
Costly, thus, do not possess competitiveness compared with other preparation method.Hydrogen peroxide method due to
Hydrogen peroxide source is cheap, and this method has the biggest captivation, and rare inorganic byproduct is formed, but
In product, content of organics exceeds nearly a hundred times than urea method.Ketazine process has small investment, product is received
Rate is high, energy consumption is low, low cost and other advantages.This method is used to prepare hydrazine hydrate both at home and abroad commonplace.
But, ketazine process can produce the waste water that salinity is the highest, and sodium chloride concentration is the highest, additionally, should
Possibly together with the Organic substance such as acetone, ketazine in waste water, COD value is the highest, belongs to relatively difficulty
The highly salt containing organic waste water of reason.
Summary of the invention
For the deficiencies in the prior art, the present invention proposes the height of a kind of preparation of hydrazine hydrate by use of ketazine and contains
Salt wastewater membrane method integrated treatment process, it is achieved that Organic substance and the high efficiency separation of inorganic salt.
The technical scheme is that the high-salt wastewater embrane method of a kind of preparation of hydrazine hydrate by use of ketazine is integrated
Processing technique, it specifically comprises the following steps that
1) high slat-containing wastewater to preparation of hydrazine hydrate by use of ketazine carries out adsorbing pretreatment, reduces COD
Value.
2) waste water after absorption is carried out microfiltration process, the water purification after using high-pressure pump to be filtered by microfiltration
Delivering to nanofiltration system and carry out concentration, trapped fluid carries out Slag treatment.
3) product water pretreated to microfiltration carries out nanofiltration process, and concentrated solution is delivered to adsorption treatment,
Per-meate side water outlet enters catalytic ozonation system.
4) waste water after catalytic ozonation processes carries out stripping process, removes volatilization with further
Property Organic substance.
5) waste water after stripping processes is delivered to salt refining.
The electrical conductivity of the high slat-containing wastewater of above-mentioned preparation of hydrazine hydrate by use of ketazine is
90000-300000 μ s/cm, CODCrFor 2500-4500mg/L；The electricity of waste water after absorption, microfiltration
Conductance is 80000-290000 μ s/cm, CODCrFor 1700-2800mg/L；Water is produced after nanofiltration
Electrical conductivity is 75000-270000 μ s/cm, CODCrFor 500-800mg/L；Through catalytic ozonation
After useless electrical conductivity of water be 75000-270000 μ s/cm, CODCrFor 60-120mg/L；Through stripping
Rear useless electrical conductivity of water is 75000-270000 μ s/cm, CODCrFor 20-50mg/L.
Preferred adsorbent is the one in silica gel, activated alumina, activated carbon, molecular sieve or any
Several combinations, dosage is 0.5-3wt.%, and adsorption time is 20-50min.
Preferably microfiltration preprocessing process uses pressure actuated device to be circulating pump, and operation pressure is
0.1-0.3MPa；Micro-filtration membrane is organic membrane or inoranic membrane, and film average pore size is 0.03-5 μm；Film group
Part is tubular membrane, rolled film or hollow-fibre membrane.
Preferably nanofiltration process uses pressure actuated device to be circulating pump, and operation pressure is 0.4-0.8MPa；
NF membrane is organic membrane or inoranic membrane, and film average pore size is 1-5nm；Membrane module is tubular membrane, volume
Formula film or hollow-fibre membrane.
The preferably oxygen air inflow of ozone oxidation is 3-15L/min, and ozone dosage is 3-10g/L.
The preferred metal oxide catalyst of catalyst, for burnings such as Fe, Mn, Ni, La, Ce, Al
One in thing, catalyst charge is the 0.1-6wt.% of reaction system.Pending water is at device
In the time of staying be 5-200min, preferably 15-100min.
Preferably stripping gas-liquid volume ratio be 200-400, pH be 9-13, stripping temperature is 30-100 DEG C,
Stripping time is 1-4h.
Beneficial effect:
The present invention is by the high slat-containing wastewater of preparation of hydrazine hydrate by use of ketazine warp after absorption, microfiltration pretreatment
Crossing high-pressure pump to be delivered to membrane filtration system and carry out nanofiltration process, the water purification of per-meate side enters ozone catalytic
Oxidation processes, the waste water after catalytic ozonation carries out stripping process, and stripping processes waste water conveying
To salt refining.Film is coupled by the present invention with catalytic ozonation, stripping process, it is achieved that high
The hydrazine hydrate of saliferous gives up the separation of Organic substance in water and inorganic salt, have that energy consumption is low, technique is advanced,
The advantages such as simple to operate, effect stability is reliable.
Accompanying drawing explanation
Fig. 1 is to be the high slat-containing wastewater embrane method integrated treatment process flow process of preparation of hydrazine hydrate by use of ketazine
Figure.
Detailed description of the invention
Embodiment 1
It is 90000 μ s/cm, COD to electrical conductivityCrHydrazine hydrate waste water for 2500mg/L adsorbs
Pretreatment, the adsorbent of employing is active carbon powder, and dosage is 0.5wt.%, adsorbs 20min
After carry out microfiltration pretreatment, the hollow-fibre membrane using membrane aperture to be 0.03 μm at transmembrane pressure is
Filtering under conditions of 0.3MPa, producing water conductivity is 80000 μ s/cm, CODCrFor 1700mg/L；
Nanofiltration membrane system will be delivered to through the pretreated penetrating fluid of microfiltration by high-pressure pump, use
Average pore size is that the ceramic alumina hollow fiber nanofiltration membrane of 5nm carries out concentration, at transmembrane pressure
Difference is for filtering under conditions of 0.6MPa, and the light electrical conductivity of water of per-meate side is 75000 μ s/cm,
CODCrFor 500mg/L；Nanofiltration per-meate side is produced water and is entered catalytic ozonation process, the catalysis of employing
Agent is that cellular oxidative aluminum loads manganese oxide, and consumption is 0.1wt.%, and oxygen air inflow is 3L/min,
Ozone dosage is 3g/L, and the time of staying is 5min, the conductance of the waste water after catalytic ozonation
Rate is 75000 μ s/cm, CODCrFor 120mg/L；Waste water after catalytic ozonation is delivered to stripping
Processing, the electrical conductivity of stripping processed waste water is 75000 μ s/cm, CODCrFor 50mg/L, stripping gas
Liquid volume ratio is 200, and pH is 13, and stripping temperature is 90 DEG C, and stripping time is 1h.
Embodiment 2
It is 300000 μ s/cm, COD to electrical conductivityCrHydrazine hydrate waste water for 4500mg/L adsorbs
Pretreatment, the adsorbent of employing is activated alumina, and dosage is 3wt.%, after absorption 50min
Carry out microfiltration pretreatment, use membrane aperture be the tubular membrane of 5 μm be the bar of 0.1MPa at transmembrane pressure
Filtering under part, producing water conductivity is 290000 μ s/cm, CODCrFor 2800mg/L；Will be through microfiltration
Pretreated penetrating fluid is delivered to nanofiltration membrane system by high-pressure pump, and employing average pore size is
The sulfonated polyphenyl sulfone rolled film of 1nm carries out concentration, under conditions of transmembrane pressure is 0.8MPa
Filtering, the light electrical conductivity of water of per-meate side is 270000 μ s/cm, CODCrFor 800mg/L；Nanofiltration
Per-meate side is produced water and is entered catalytic ozonation process, and the catalyst of employing is that cellular oxidative aluminum loads oxygen
Changing cerium, consumption is 6wt.%, and oxygen air inflow is 15L/min, and ozone dosage is 10g/L, stops
Staying the time is 100min, and the useless electrical conductivity of water after catalytic ozonation is 270000 μ s/cm,
CODCrFor 120mg/L；Waste water after catalytic ozonation is delivered to stripping and processes, waste water after stripping
Electrical conductivity be 270000 μ s/cm, CODCrFor 20mg/L, stripping gas-liquid volume ratio is 400, pH
Being 9, stripping temperature is 30 DEG C, and stripping time is 4h.
Embodiment 3
It is 190000 μ s/cm, COD to electrical conductivityCrHydrazine hydrate waste water for 3050mg/L adsorbs
Pretreatment, the adsorbent of employing is inorganic silica gel, and dosage is 0.5wt.%, after absorption 40min
Carry out microfiltration pretreatment, use membrane aperture be the tubular membrane of 3 μm be the bar of 0.2MPa at transmembrane pressure
Filtering under part, producing water conductivity is 170000 μ s/cm, CODCrFor 2570mg/L；Will be through microfiltration
Pretreated penetrating fluid is delivered to nanofiltration membrane system by high-pressure pump, and employing average pore size is
The sulfonated polyether sulfone hollow-fibre membrane of 2nm carries out concentration, is the bar of 0.5MPa at transmembrane pressure
Filtering under part, the light electrical conductivity of water of per-meate side is 155200 μ s/cm, CODCrFor 629mg/L；
Nanofiltration per-meate side is produced water and is entered catalytic ozonation process, and the catalyst of employing is that cellular oxidative aluminum is born
Carrying lanthana, consumption is 5wt.%, and oxygen air inflow is 7.3L/min, and ozone dosage is 6g/L,
The time of staying is 40min, and the useless electrical conductivity of water after catalytic ozonation is 155200 μ s/cm,
CODCrFor 77mg/L；Waste water after catalytic ozonation is delivered to stripping and processes, the electricity of de-rear waste water
Conductance is 155200 μ s/cm, CODCrFor 32mg/L, stripping gas-liquid volume ratio is 350, and pH is 10,
Stripping temperature is 50 DEG C, and stripping time is 3h.
Claims (7)
1. a high slat-containing wastewater embrane method integrated treatment process for preparation of hydrazine hydrate by use of ketazine, it specifically comprises the following steps that
1) high slat-containing wastewater to preparation of hydrazine hydrate by use of ketazine carries out adsorbing pretreatment, reduces COD value；
2) waste water after absorption being carried out microfiltration process, the water purification after using high-pressure pump to be filtered by microfiltration is delivered to nanofiltration system and is carried out concentration, and trapped fluid carries out Slag treatment；
3) product water pretreated to microfiltration carries out nanofiltration process, and concentrated solution is delivered to adsorption treatment, and per-meate side water outlet enters catalytic ozonation system；
4) waste water after catalytic ozonation processes carries out stripping process, to remove volatile organic matter further；
5) waste water after stripping processes is delivered to salt refining.
The high slat-containing wastewater embrane method integrated treatment process of a kind of preparation of hydrazine hydrate by use of ketazine, it is characterised in that the electrical conductivity of the high slat-containing wastewater of preparation of hydrazine hydrate by use of ketazine is 90000-300000 μ s/cm, CODCrFor 2500-4500mg/L；After absorption, microfiltration, useless electrical conductivity of water is 80000-290000 μ s/cm, CODCrFor 1700-2800mg/L；Producing electrical conductivity of water after nanofiltration is 75000-270000 μ s/cm, CODCrFor 500-800mg/L；Useless electrical conductivity of water after catalytic ozonation is 75 000-270000 μ s/cm, CODCrFor 60-120mg/L；After stripping, useless electrical conductivity of water is 750 00-270000 μ s/cm, CODCrFor 20-50mg/L.
Technique the most according to claim 1, it is characterised in that adsorbent is a kind of or the most several combination in silica gel, activated alumina, activated carbon, molecular sieve, dosage is 0.5-3wt.%, and adsorption time is 20-50min.
Technique the most according to claim 1, it is characterised in that microfiltration preprocessing process uses pressure actuated device to be circulating pump, and operation pressure is 0.1-0.3MPa；Micro-filtration membrane is organic membrane or inoranic membrane, and film average pore size is 0.03-5 μm；Membrane module is tubular membrane, rolled film or hollow-fibre membrane.
Technique the most according to claim 1, it is characterised in that nanofiltration processing procedure uses pressure actuated device to be circulating pump, and operation pressure is 0.4-0.8MPa；NF membrane is organic membrane or inoranic membrane, and film average pore size is 1-5nm；Membrane module is tubular membrane, rolled film or hollow-fibre membrane.
Technique the most according to claim 1, it is characterised in that the oxygen air inflow of ozone oxidation is 3-15L/min, ozone dosage is 3-10g/L；Catalyst is the one in the metal-oxides such as Fe, Mn, Ni, La, Ce, Al, and catalyst charge is the 0.1-6wt.% of reaction system；The pending water time of staying in a device is 5-200min.
Technique the most according to claim 1, it is characterised in that stripping gas-liquid volume ratio be 200-400, pH be 9-13, stripping temperature is 30-90 DEG C, and stripping time is 1-4h.
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| CN107721023A (en) * | 2017-11-22 | 2018-02-23 | 天津海泽惠科技发展有限公司 | A kind of hydrazine hydrate wastewater treatment equipment and its technique |
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