CN114940546A - Treatment method for recycling hydrazine hydrate industrial wastewater to prepare caustic soda by electrolyzing salt solution - Google Patents
Treatment method for recycling hydrazine hydrate industrial wastewater to prepare caustic soda by electrolyzing salt solution Download PDFInfo
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- CN114940546A CN114940546A CN202210465596.7A CN202210465596A CN114940546A CN 114940546 A CN114940546 A CN 114940546A CN 202210465596 A CN202210465596 A CN 202210465596A CN 114940546 A CN114940546 A CN 114940546A
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 50
- 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 47
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 43
- 235000011121 sodium hydroxide Nutrition 0.000 title claims abstract description 36
- 239000012266 salt solution Substances 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- 239000012530 fluid Substances 0.000 claims abstract description 57
- 230000000149 penetrating effect Effects 0.000 claims abstract description 36
- 238000001728 nano-filtration Methods 0.000 claims abstract description 34
- 239000002351 wastewater Substances 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 58
- 239000012528 membrane Substances 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- 238000003860 storage Methods 0.000 claims description 28
- 230000003197 catalytic effect Effects 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000108 ultra-filtration Methods 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 16
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 15
- 229910001424 calcium ion Inorganic materials 0.000 claims description 15
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 claims description 9
- 238000006731 degradation reaction Methods 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/20—Preparation by reacting oxides or hydroxides with alkali metal salts
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- 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
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- 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
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- 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
- C02F1/722—Oxidation by peroxides
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- 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
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- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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- C02F2209/20—Total organic carbon [TOC]
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Abstract
A treatment method for recycling hydrazine hydrate industrial wastewater to prepare caustic soda from electrolytic salt solution belongs to the technical field of wastewater treatment, and can solve the problems that the treatment effect of organic matters in the wastewater is poor, the organic matters in high-concentration salt in the wastewater cannot be directly and effectively degraded, the wastewater resources are recycled, and the resources are wasted in the existing hydrazine hydrate industrial wastewater treatment method. The method has high removal rate of organic matters in the wastewater, and can recycle nanofiltration penetrating fluid treated by resin to electrolytic salt solution for preparing caustic soda, thereby realizing high-added-value resource recycling while treating the hydrazine hydrate industrial wastewater.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a treatment method for recycling hydrazine hydrate industrial wastewater to prepare caustic soda by electrolyzing saline solution.
Background
Hydrazine hydrate (N) 2 H 4 . H 2 O) is a colorless and transparent oily liquid with light ammonia smell, has strong polarity, reducibility, alkalinity and hygroscopicity, is an important chemical raw material and a chemical intermediate, and has wide application in the industries of medicine, pesticide, chemistry and military industry.
The preparation method of hydrazine hydrate is Raschig method and urea method, the two methods respectively take ammonia and urea as nitrogen source and sodium hypochlorite as oxidant to react to generate N 2 H 4 . H 2 O, in the production process, waste water is generated, so that a large amount of NaCl and organic matters exist in the waste water, the waste water has high toxicity, and if the waste water enters a water body without being effectively treated, the waste water can cause serious harm to the environment.
At present, the method for treating hydrazine hydrate industrial wastewater is reported by documents and mainly adopts methods such as an adsorption method, a membrane separation method, ozone oxidation and the like, a single treatment process has poor treatment effect on organic matters in the wastewater, and the organic matters in high-concentration salt in the wastewater cannot be directly and effectively degraded, so that the wastewater resource recycling is realized, and the resource waste is caused. In order to realize the reutilization of salt resources in water, CN 113562913A adopts resin and three-phase catalytic oxidation to remove organic matters in wastewater, and then recovers salt through evaporative crystallization, wherein a chlorine dioxide oxidizing agent is adopted in a three-phase catalytic oxidation device, the treatment effect is poorer than that of Fenton-like (hydrogen peroxide catalytic oxidation method), high-valence ions (calcium ions, magnesium ions and the like) in a solution influence the quality of evaporative crystallized salt, and the utilization range is limited.
Disclosure of Invention
The invention provides a treatment method for preparing caustic soda by recycling industrial wastewater of hydrazine hydrate to electrolytic salt solution, aiming at the problems that the treatment effect of organic matters in the wastewater is poor, the organic matters in high-concentration salt in the wastewater cannot be directly and effectively degraded, the resource recycling of the wastewater is realized, and the resource waste is caused in the existing treatment method for the industrial wastewater of hydrazine hydrate.
The invention adopts the following technical scheme:
a treatment method for recycling hydrazine hydrate industrial wastewater to prepare caustic soda by electrolyzing saline solution comprises the following steps:
firstly, feeding hydrazine hydrate industrial wastewater into a storage tank, wherein the concentration of NaCl in the wastewater is 200-400 g/L, and the value of organic matters in a solution, expressed as TOC, is 50-500 mg/L;
secondly, removing organic matters from the hydrazine hydrate industrial wastewater in the storage tank through a catalytic oxidation device, adding hydrogen peroxide in the process of removing the organic matters, wherein the TOC value of the solution treated by the catalytic oxidation device is 15-150 mg/L, and the degradation rate reaches 60-98%;
thirdly, feeding the solution treated by the catalytic oxidation device into an ultrafiltration device, wherein the turbidity of the solution treated by the ultrafiltration membrane is lower than 10 NTU;
fourthly, feeding the solution treated by the ultrafiltration device into nanofiltration equipment, and treating the solution by using a nanofiltration membrane to obtain penetrating fluid and trapped fluid, wherein the TOC value of the penetrating fluid output by the nanofiltration equipment is 10-150 mg/L, the concentration of calcium and magnesium ions is lower than 10 mg/L, the TOC value of the trapped fluid is 80-1500 mg/L, and the trapped fluid returns to a wastewater storage tank;
fifthly, the penetrating fluid obtained through the treatment of the nanofiltration equipment is sent into a resin adsorption tower, organic matters in the penetrating fluid are further removed, the TOC value in the solution is 0-5 mg/L, the concentration reduction value of calcium and magnesium ions is 0.1-1 mg/L, and the penetrating fluid is sent into a purified salt water storage tank to be used as electrolytic salt water to prepare caustic soda.
Further, in the second step, the concentration of the hydrogen peroxide is 0-500ppm, and the space velocity of the hydrogen peroxide is 0.5-10h -1 The pH value of the entering solution is 3-12, and the reaction temperature is 15-45 ℃.
Further, in the third step, the ultrafiltration membrane is an organic composite roll-up membrane, the pore diameter of a membrane core is 200-2000 dal, the pressure is 2-6 MPa, the operation temperature is 5-45 ℃, and the pH value of inlet water is 3-12.
And further, in the fourth step, the nanofiltration membrane is an organic composite roll-up membrane, the aperture of a membrane core is 100-1000 dal, the equipment pressure is 2-6 MPa, the operation temperature is 5-45 ℃, and the pH value of inlet water is 3-12.
Further, the method can be used for preparing a novel materialIn the fifth step, the space velocity adopted by the resin adsorption tower is 0.5-8 h -1 The pH value of the entering solution is 3-12, the reaction temperature is 5-45 ℃, and the type of the resin is adsorption resin.
In order to realize the high value-added recycling of the hydrazine hydrate wastewater, the invention recycles the treated hydrazine hydrate wastewater to the electrolytic salt solution for preparing caustic soda. The production method mainly comprises an electrolytic salt solution ion membrane method, an electrolytic bath has high requirements on organic matters (TOC), calcium, magnesium and other ion impurities in a salt solution in the preparation process, therefore, in order to greatly reduce the content of the organic matters, a catalytic oxidation device adopts hydrogen peroxide as an oxidant, a porous solid transition metal oxide is a hydroxyl-generating free radical catalyst, so that the degradation rate of the organic matters reaches 60% -98%, the residual organic matters are retained by 50% -60% through an ultrafiltration and nanofiltration device, the impurities such as calcium, magnesium and other ions are intercepted, finally, the low-concentration organic matters in water are removed through special macroporous resin, and the salt solution purity reaches the production index of the electrolytic salt solution through three-level gradual degradation, so that the high-added-value utilization of the high-concentration salt solution containing the organic matters is realized.
The invention has the following beneficial effects:
1. a treatment method for recycling hydrazine hydrate industrial wastewater to electrolytic salt solution for preparing caustic soda adopts a treatment process of combining catalytic oxidation, nanofiltration and resin to degrade organic matters in three stages to remove organic matters and high-valence ions in the hydrazine hydrate industrial wastewater, so that the solution after resin treatment can reach the standard of electrolytic salt solution for preparing caustic soda.
2. Compared with single adsorption, membrane separation, ozone oxidation and other methods, the treatment method for preparing the caustic soda from the hydrazine hydrate industrial wastewater recycled to the electrolytic salt solution has good treatment effect on organic matters, the treated water can directly reach the standard of preparing the caustic soda from the electrolytic salt solution, the cost of preparing the caustic soda from the electrolytic salt solution is reduced, and the high-added-value resource reutilization is realized.
3. The invention discloses a method for treating hydrazine hydrate industrial wastewater by recycling electrolytic salt solution to prepare caustic soda, which is a novel combined idea and method for treating the hydrazine hydrate industrial wastewater, and meanwhile, the method can provide a good reference for treating and recycling similar pollutants in the future.
Drawings
FIG. 1 is a process flow diagram of the treatment method of the present invention.
Detailed Description
The invention is further described with reference to the following figures and specific examples, but the scope of the claims is not limited thereto.
Example 1
Referring to fig. 1, a treatment method for recycling hydrazine hydrate industrial wastewater to electrolytic salt solution for preparing caustic soda comprises the following steps:
(1) feeding hydrazine hydrate industrial wastewater into a storage tank, wherein the concentration of NaCl in the wastewater is 200 g/L, and the value of organic matters (expressed as TOC) in a solution is 80 mg/L.
(2) Removing organic matters from the hydrazine hydrate industrial wastewater in the storage tank by a catalytic oxidation device, adding hydrogen peroxide in the process of removing the organic matters, wherein the TOC value of the solution treated by the catalytic oxidation device is 21 mg/L, and the degradation rate reaches 73.75%.
(3) And (3) feeding the solution treated by the catalytic oxidation device into an ultrafiltration device, wherein the turbidity of the solution treated by the ultrafiltration membrane is 3.7 NTU.
(4) And (3) feeding the solution treated by the ultrafiltration device into nanofiltration equipment, treating the solution by using a nanofiltration membrane to obtain penetrating fluid and trapped fluid, wherein the TOC value of the penetrating fluid produced by the nanofiltration equipment is 11.6 mg/L, the concentration of calcium and magnesium ions is 6.7 mg/L, the TOC value of the trapped fluid is 83.2 mg/L, and the trapped fluid returns to a wastewater storage tank.
(5) And (3) conveying the penetrating fluid obtained by the treatment of the nanofiltration equipment into a resin adsorption tower, further removing organic matters in the penetrating fluid, conveying the penetrating fluid into a purified salt water storage tank for preparing caustic soda by electrolyzing salt water, wherein the TOC value in the solution is 0.8 mg/L, and the concentration reduction value of calcium and magnesium ions is 0.13 mg/L.
Example 2
Referring to fig. 1, a treatment method for recycling hydrazine hydrate industrial wastewater to electrolytic salt solution for preparing caustic soda comprises the following steps:
(1) the hydrazine hydrate industrial wastewater is sent into a storage tank, the concentration of NaCl in the wastewater is 240 g/L, and the value of organic matters (expressed as TOC) in the solution is 130 mg/L.
(2) Removing organic matters from the hydrazine hydrate industrial wastewater in the storage tank by a catalytic oxidation device, adding hydrogen peroxide in the process of removing the organic matters, wherein the TOC value of the solution treated by the catalytic oxidation device is 28 mg/L, and the degradation rate reaches 78.46%.
(3) And (3) feeding the solution treated by the catalytic oxidation device into an ultrafiltration device, wherein the turbidity of the solution treated by the ultrafiltration membrane is 4.8 NTU.
(4) And (3) feeding the solution treated by the ultrafiltration device into nanofiltration equipment, treating the solution by using a nanofiltration membrane to obtain penetrating fluid and trapped fluid, wherein the TOC value of the penetrating fluid produced by the nanofiltration equipment is 14.2 mg/L, the concentration of calcium and magnesium ions is 7.3 mg/L, the TOC value of the trapped fluid is 93.7 mg/L, and the trapped fluid returns to a wastewater storage tank.
(5) And (3) conveying the penetrating fluid obtained by the treatment of the nanofiltration equipment into a resin adsorption tower, further removing organic matters in the penetrating fluid, conveying the penetrating fluid into a purified salt water storage tank for preparing caustic soda by electrolyzing salt water, wherein the TOC value of the solution is 1.6 mg/L, and the concentration reduction value of calcium and magnesium ions is 0.27 mg/L.
Example 3
Referring to fig. 1, a treatment method for recycling hydrazine hydrate industrial wastewater to electrolytic salt solution for preparing caustic soda comprises the following steps:
(1) the hydrazine hydrate industrial wastewater is sent into a storage tank, the NaCl concentration in the wastewater is 280 g/L, and the organic matter (expressed as TOC) value in the solution is 240 mg/L.
(2) Removing organic matters from the hydrazine hydrate industrial wastewater in the storage tank by a catalytic oxidation device, adding hydrogen peroxide in the process of removing the organic matters, wherein the TOC value of the solution treated by the catalytic oxidation device is 35 mg/L, and the degradation rate reaches 85.42%.
(3) And (3) feeding the solution treated by the catalytic oxidation device into an ultrafiltration device, wherein the turbidity of the solution treated by the ultrafiltration membrane is 5.3 NTU.
(4) And (3) feeding the solution treated by the ultrafiltration device into nanofiltration equipment, treating the solution by using a nanofiltration membrane to obtain penetrating fluid and trapped fluid, wherein the TOC value of the penetrating fluid produced by the nanofiltration equipment is 21.8 mg/L, the concentration of calcium and magnesium ions is reduced to 7.6 mg/L, the TOC value of the trapped fluid is 126.1 mg/L, and the trapped fluid returns to a wastewater storage tank.
(5) And (3) conveying the penetrating fluid obtained by the treatment of the nanofiltration equipment into a resin adsorption tower, further removing organic matters in the penetrating fluid, conveying the penetrating fluid into a purified salt water storage tank for preparing caustic soda by electrolyzing salt water, wherein the TOC value of the solution is 2.5 mg/L and the reduction value of the concentration of calcium and magnesium ions is 0.43 mg/L.
Example 4
Referring to fig. 1, a treatment method for recycling hydrazine hydrate industrial wastewater to electrolytic salt solution for preparing caustic soda comprises the following steps:
(1) feeding hydrazine hydrate industrial wastewater into a storage tank, wherein the concentration of NaCl in the wastewater is 320 g/L, and the value of organic matters (expressed as TOC) in the solution is 368 mg/L.
(2) Removing organic matters from the hydrazine hydrate industrial wastewater in the storage tank by a catalytic oxidation device, adding hydrogen peroxide in the process of removing the organic matters, wherein the TOC value of the solution treated by the catalytic oxidation device is 41 mg/L, and the degradation rate reaches 88.86%.
(3) And (3) feeding the solution treated by the catalytic oxidation device into an ultrafiltration device, wherein the turbidity of the solution treated by the ultrafiltration membrane is 5.2 NTU.
(4) And (3) feeding the solution treated by the ultrafiltration device into nanofiltration equipment, treating the solution by using a nanofiltration membrane to obtain penetrating fluid and trapped fluid, wherein the TOC value of the penetrating fluid produced by the nanofiltration equipment is 22.5 mg/L, the concentration of calcium and magnesium ions is 8.5 mg/L, the TOC value of the trapped fluid is 254.3 mg/L, and the trapped fluid returns to a wastewater storage tank.
(5) And (3) sending penetrating fluid obtained by the treatment of the nanofiltration equipment into a resin adsorption tower, further removing organic matters in the penetrating fluid, sending the penetrating fluid into a purified salt water storage tank for preparing caustic soda by electrolyzing salt water, wherein the TOC value of the solution is 2.9 mg/L, and the reduction value of the calcium and magnesium ion concentration is 0.69 mg/L.
Example 5
Referring to fig. 1, a treatment method for recycling hydrazine hydrate industrial wastewater to electrolytic salt solution for preparing caustic soda comprises the following steps:
(1) the hydrazine hydrate industrial wastewater is sent into a storage tank, the concentration of NaCl in the wastewater is 400 g/L, and the value of organic matters (expressed as TOC) in the solution is 475 mg/L.
(2) Removing organic matters from the hydrazine hydrate industrial wastewater in the storage tank by a catalytic oxidation device, adding hydrogen peroxide in the process of removing the organic matters, wherein the TOC value of the solution treated by the catalytic oxidation device is 146 mg/L, and the degradation rate reaches 61.26%.
(3) And (3) feeding the solution treated by the catalytic oxidation device into an ultrafiltration device, wherein the turbidity of the solution treated by the ultrafiltration membrane is 6.9 NTU.
(4) And (3) feeding the solution treated by the ultrafiltration device into nanofiltration equipment, and treating the solution by using a nanofiltration membrane to obtain penetrating fluid and trapped fluid, wherein the TOC value of the penetrating fluid produced by the nanofiltration equipment is 42.5 mg/L, the concentration of calcium and magnesium ions is 9.4 mg/L, the TOC value of the trapped fluid is 752.3 mg/L, and the trapped fluid returns to a wastewater storage tank.
(5) And (3) conveying the penetrating fluid obtained by the treatment of the nanofiltration equipment into a resin adsorption tower, further removing organic matters in the penetrating fluid, conveying the penetrating fluid into a purified salt water storage tank for preparing caustic soda by electrolyzing salt water, wherein the TOC value of the solution is 4.5 mg/L, and the concentration reduction value of calcium and magnesium ions is 0.84 mg/L.
In addition, in order to achieve better technical effects, the technical solutions in the above embodiments may be combined arbitrarily to meet various requirements of practical applications.
According to the specific embodiment, the catalytic oxidation device, the nanofiltration device and the resin device are adopted to remove organic matters and high-valence ions in the hydrazine hydrate industrial wastewater, so that the solution after resin treatment can reach the standard of preparing caustic soda by electrolyzing the salt water.
Compared with single adsorption, membrane separation, ozone oxidation and other methods, the treatment method for preparing the caustic soda from the hydrazine hydrate industrial wastewater recycled to the electrolytic salt solution has good treatment effect on organic matters, the treated water can directly reach the standard of preparing the caustic soda from the electrolytic salt solution, the cost of preparing the caustic soda from the electrolytic salt solution is reduced, and high value-added resources are recycled.
The invention discloses a method for treating hydrazine hydrate industrial wastewater by recycling electrolytic salt solution to prepare caustic soda, which is a novel combined idea and method for treating the hydrazine hydrate industrial wastewater, and meanwhile, the method can provide a good reference for treating and recycling similar pollutants in the future.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (5)
1. A treatment method for recycling hydrazine hydrate industrial wastewater to prepare caustic soda by electrolyzing salt water is characterized by comprising the following steps: the method comprises the following steps:
firstly, feeding hydrazine hydrate industrial wastewater into a storage tank, wherein the concentration of NaCl in the wastewater is 200-400 g/L, and the value of organic matters in a solution, expressed as TOC, is 50-500 mg/L;
secondly, removing organic matters from the hydrazine hydrate industrial wastewater in the storage tank through a catalytic oxidation device, adding hydrogen peroxide in the process of removing the organic matters, wherein the TOC value of the solution treated by the catalytic oxidation device is 15-150 mg/L, and the degradation rate reaches 60-98%;
thirdly, feeding the solution treated by the catalytic oxidation device into an ultrafiltration device, wherein the turbidity of the solution treated by the ultrafiltration membrane is lower than 10 NTU;
fourthly, feeding the solution treated by the ultrafiltration device into nanofiltration equipment, and treating the solution by using a nanofiltration membrane to obtain penetrating fluid and trapped fluid, wherein the TOC value of the penetrating fluid output by the nanofiltration equipment is 10-150 mg/L, the concentration of calcium and magnesium ions is lower than 10 mg/L, the TOC value of the trapped fluid is 80-1500 mg/L, and the trapped fluid returns to a wastewater storage tank;
fifthly, the penetrating fluid obtained through the treatment of the nanofiltration equipment is sent into a resin adsorption tower, organic matters in the penetrating fluid are further removed, the TOC value in the solution is 0-5 mg/L, the concentration reduction value of calcium and magnesium ions is 0.1-1 mg/L, and the penetrating fluid is sent into a purified salt water storage tank to be used as electrolytic salt water to prepare caustic soda.
2. According to claimThe treatment method for recycling hydrazine hydrate industrial wastewater to electrolyze salt solution to prepare caustic soda, which is characterized by comprising the following steps: in the second step, the concentration of the hydrogen peroxide is 0-500ppm, and the airspeed of the hydrogen peroxide is 0.5-10h -1 The pH value of the entering solution is 3-12, and the reaction temperature is 15-45 ℃.
3. The method for treating hydrazine hydrate industrial wastewater recycled to the caustic soda production by electrolysis of saline solution according to claim 1, characterized by comprising the following steps: in the third step, the ultrafiltration membrane is an organic composite roll-up membrane, the pore diameter of a membrane core is 200-2000 dal, the pressure is 2-6 MPa, the operating temperature is 5-45 ℃, and the pH value of inlet water is 3-12.
4. The method for treating hydrazine hydrate industrial wastewater recycled to the caustic soda preparation by electrolysis of saline solution according to claim 1, characterized in that: in the fourth step, the nanofiltration membrane is an organic composite roll-up membrane, the aperture of a membrane core is 100-1000 dal, the equipment pressure is 2-6 MPa, the operation temperature is 5-45 ℃, and the pH value of inlet water is 3-12.
5. The method for treating hydrazine hydrate industrial wastewater recycled to the caustic soda preparation by electrolysis of saline solution according to claim 1, characterized in that: in the fifth step, the space velocity adopted by the resin adsorption tower is 0.5-8 h -1 The pH value of the entering solution is 3-12, the reaction temperature is 5-45 ℃, and the type of the resin is adsorption resin.
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