CN110386728A - A kind of tubular type free-radical oxidation handles the integral process of the high COD industrial wastewater of high salinity - Google Patents
A kind of tubular type free-radical oxidation handles the integral process of the high COD industrial wastewater of high salinity Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 19
- 239000002351 wastewater Substances 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910001868 water Inorganic materials 0.000 claims abstract description 43
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- 238000012545 processing Methods 0.000 claims abstract description 19
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000009279 wet oxidation reaction Methods 0.000 claims description 15
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000006731 degradation reaction Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 239000010865 sewage Substances 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 6
- 230000000813 microbial effect Effects 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- -1 salt compounds Chemical class 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 238000005299 abrasion Methods 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- 230000003139 buffering effect Effects 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000012423 maintenance Methods 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 239000001963 growth medium Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000013612 plasmid Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- C02F1/001—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
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides the integral process that a kind of tubular type free-radical oxidation handles the high COD industrial wastewater of high salinity, by settling, evaporating crystallisation by cooling, degrade with water pot water distribution, tubular type free-radical oxidation, microorganism, reverse osmosis membrane processing, utilize integral process of the invention, realize high saliferous organic wastewater with high concentration treatment zero draining, it solves in the prior art, it solves the problems, such as that operating cost is high in the prior art, processing is halfway, the high-COD waste water with high salt of salt content 25wt% or more can be handled；Tubular type free-radical oxidation handles the integral process of the high COD industrial wastewater of high salinity, heat energy self-supporting in realization system, using the heat generated in wet type reaction process, in addition to maintenance wet type reaction is from the mount of using heat, the heating to evaporator can be realized in the form of rich producing steam, saved the energy.
Description
Technical field
The present invention relates to sewage treatment field, in particular to a kind of tubular type free-radical oxidation handles the high COD industry of high salinity
The integral process of waste water.
Background technique
In Chinese society economic development and urbanization process, it is sustainable that water scarcity is being increasingly becoming restriction China
One of principal element of development strategy.In recent years, with the plant-scale continuous increase in China, industrial water consumption increases sharply.Meanwhile
It generates wastewater flow rate also to increase rapidly, brings huge challenge to current wastewater treatment and recovery and utilization technology.Industrial wastewater
Such as direct emission, serious pollution will be generated to surrounding soil, water body environment.Waste water is after processing qualification is up to standard, if do not recycled
It utilizes, then causes water resource waste, aggravate shortage of water resources.For high-salt wastewater, due to lacking technology, feasibility economically
It is most of to take the outer discharge method of dilution with reliability.This method not only cannot really reduce the total emission volumn of pollutant, and
The discharge of the waste of fresh water, especially brine waste is caused, fresh water water resource mineralising and alkalization of soils are bound to cause.With foreign countries
The desalting technology level of high-salt wastewater " zero-emission " or " become zero-emission " is compared, and there is larger gap in China.Therefore, how warp is developed
It helps effective high-salt wastewater desalting processing technology, promotes the resource utilization of high-salt wastewater, and solve water resource circulation
The bottleneck problem utilized.
For wastewater biochemical processing, high-salt wastewater refers to containing organic matter and at least total dissolved solidss (TDS)
Mass fraction is greater than 3.5% waste water.Because, in addition to containing organic pollutant, also containing great amount of soluble in this kind of waste water
Inorganic salts, such as Cl-、Na+、SO4 2-、Ca2+Deng.So this kind of waste water is usually the limit of biochemical treatment.It is reported that in foreign countries
Has the phenol wastewater using the special salt tolerant Halophiles processing saliferous 15% raised and train；At home, also about using Halophiles
It can handle the report of 5% waste water of saliferous.For this kind of waste water other than sea water desalination generates, other are mainly derived from following field:
1. Chemical Manufacture, chemical reaction is incomplete or chemically reacts by-product, especially produced in the chemical products production process such as dyestuff, pesticide
Raw a large amount of high COD, toxic wastewater with high salt；2. wastewater treatment, in wastewater treatment process, the addition of water treatment agent and acid, alkali
Bring mineralising, and the concentrate of most of " light " water recycling and generation, can all increase the concentration of solubility salt, form institute
" high salinity waste water " for being difficult to biochemical treatment of meaning.As it can be seen that this kind of brine waste have compared with Normal wastewater to environment it is bigger
Pollution.
Currently, the common processing method for highly concentrated organic wastewater with difficult degradation thereby with high salt has: incineration method, evaporation desalination, film point
From, ion-exchange, electrochemical process and tubular type free-radical oxidation method.Incineration method refers to useless Organic substance in water at 800~1000 DEG C
Under the conditions of with oxygen in air carry out vigorous reaction, release energy and generate high-temp combustion gas and the stable solid residue of property,
But operating cost is higher, and incineration method can generate oxysulfide, the exhaust gas such as nitrogen oxides and dioxin.Moreover, high saliferous has
Machine waste water influences the service life of equipment to the seriously corroded of burning facility.Evaporating desalination is to be added using steam to waste water
Heat makes most of water evaporation and makes the inorganic method salted out.It, can not will be inorganic but when organic concentration is higher in waste water
Salt and organic matter are effectively separated, so that a large amount of thick fluids are generated, it is high as dangerous waste processing cost.UF membrane is basis
Separated object plasmid diameter is of different sizes, the method for separating different material as driving force using pressure.But have when in waste water
When machine object content is higher, film can be polluted；Ingredient complicated in waste water also influences whether organic matter and inorganic salts simultaneously
Separating effect.A kind of reversible chemical reaction for ion-exchange, that is, carried out between liquid phase intermediate ion and solid phase intermediate ion.Due to tree
The exchange capacity of rouge is limited, and salinity is excessively high to greatly increase resin regeneration number, reduces ion-exchange effect, and this method is not applicable
In the waste water that processing salinity is excessively high.Electrochemical process is to generate electric field by applying electric current, to make the zwitterion in solution
Displacement, inorganic salts are precipitated at the two poles of the earth, while also having certain removal effect to organic matter.But electrochemical process is not suitable for
The processing of high concentrated organic wastewater, because as the expense that organic matter and salt content increase electrochemical process processing waste water can mention significantly
It is high.
Tubular type free-radical oxidation method is grown up on the basis of wet air oxidation.Wet air oxidation is beauty
Zimmer~man of state is in exploitation in 1994, also known as WAO method.The processing method that catalyst is added in WAO method is then referred to as
For tubular type free-radical oxidation method, abbreviation WACO method.It refers under high temperature (200~280 DEG C), high pressure (2~8MPa), with oxygen-enriched
Gas or oxygen are oxidant, using the catalytic action of catalyst, accelerate the respiratory reaction between useless Organic substance in water and oxidant,
Make the organic matter in waste water and is oxidized to CO containing poisonous substances such as N, S2、N2、SO2、H2O reaches the purpose of purification.It is oxygen-containing to high chemistry
The various industrial organic waste waters of amount or the compound that cannot be degraded containing biochemical method, COD removal rate reach 99% or more, it is no longer necessary to
It is post-processed, only through single treatment i.e. up to discharge standard.However current industrialization tubular type free-radical oxidation catalyst is equal
Not salt tolerant (haloid, sulfate, phosphate etc.), wherein loss of active component and irreversible can occur for catalyst in high-chloride wastewater
Intoxicating phenomenon seriously affects catalyst activity.Therefore a kind of resistance to salt catalyst high concentrated organic wastewater with high salt for processing is developed
It is particularly significant, while the industrial applications range of tubular type free-radical oxidation can be expanded.
In conclusion being directed to organic wastewater with difficult degradation thereby with high salt at present, there are no a kind of at low cost, high treating effect techniques
Method.Conventional method is high there are processing cost and there are secondary pollution (generating dangerous waste and exhaust gas), is unable to reach environmental requirement etc.
Problem.
Summary of the invention
The problem that the present invention is high for existing organic wastewater with difficult degradation thereby processing cost with high salt, treatment effect is bad, provides one
Kind tubular type free-radical oxidation handles the integral process of the high COD industrial wastewater of high salinity, and salinity is up to the high COD of 25wt% or more
Waste water, after treatment, it can be achieved that zero emission of wastewater treatment.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: a kind for the treatment of process of used water difficult to degradate with high salt, packet
Include the following steps:
S1, settling sand removing will be carried out in high salt, high-COD waste water importing waste water buffer pool, isolates the sand etc. of bulky grain
Substance, to avoid the sand in sewage to the abrasion of pump, the blocking of pipe network, interference even destroys biochemical treatment process；
S2, using sewage pump by waste water buffer in waste water import evaporator in, be evaporated-crystallisation by cooling, pass through steaming
High-salt wastewater is concentrated in hair, while obtaining condensed water and concentrate, cools down to concentrate, to make solvable in high-salt wastewater
Property salts substances Crystallization Separation come out, crystallization salt compounds and crystalline mother solution are obtained by filtration；
S3, crystalline mother solution is added in water distributing trough, is adjusted to the salinity in water distributing trough using the condensed water in evaporator
Between 10wt%-15wt%；
S4, the sewage in water distributing trough is imported into wet oxidation reactor, carries out wet oxidation at a certain temperature, given up
Larger molecular organics in water are by strong oxidizer oxygenolysis, and double bond fracture in organic constitution is oxidized to small by macromolecular
Molecule, small molecule are further oxidized to carbon dioxide and water, greatly improve COD sharp fall BOD/COD value；
S4, it is importing directly into microbial degradation pond from the waste water that wet oxidation reactor excludes and carries out microbial degradation；
S5, degradation solution import reverse osmosis membrane processing device and carry out extracting rate, reverse osmosis appears laggard after the filtering of biological carbon filter bed
Guild uses, and reverse osmosis concentrated water with high salt enters low-temperature evaporation crystallization, and the Nacl of generation can be recycled.
Preferably, heat source derives from the wet oxidation reactor in step S4 in evaporator in step S2；
Preferably, the 15~35% of the preferred waste water total amount of the evaporation capacity of the waste water in step S2；
Preferably, in the distribution reservoir in step S3 be equipped with waste water salinity detector, and waste water salinity detector with it is micro-
Type computer controller is connected, and is controlled using microcomputer controller and condensation water quantity is added.
Preferably, wet oxidation reactor is free-radical generator in step S4, and is mounted in free-radical generator multiple
Close catalyst；It is further preferred that the free-radical generator include pressure-air feeding device, the pressure-air into
Expect that device includes air compressor machine, high-pressure buffering pot and air flow meter.
Preferably, the composite catalyst is LaMnxCo1-xO3Perovskite type catalyst, wherein the range of x value is x=
0.01~0.2；
Preparation method includes the following steps:
1) soluble-salt of the soluble-salt of lanthanum, the soluble-salt of manganese and cobalt is stoichiometrically weighed, and is dissolved in certain
In the deionized water of amount, configure mixed salt solution, be then added a certain amount of citric acid, stirring to be completely dissolved to be formed it is molten
Glue；
2) colloidal sol is dried into moisture, be cooled to room temperature, be fully ground sieving；
3) powder after sieving is added in calciner plant, under air atmosphere, carries out microwave heating calcining to get having
LaMnxCo1-xO3Type perovskite catalyst.
Preferably, the salt tolerant Halophiles in step S5 is that the high-salt wastewater screening for being 10-15wt% using concentration is cultivated
The Facultative Halophiles with height endurability.
Preferably, the material of reverse osmosis membrane is cellulose acetate, polyamide, polyimides etc., operation pressure in step S5
Power is preferably 1.5-2.5Mpa.
Compared with prior art, beneficial effects of the present invention:
1) integral process of the invention is utilized, high saliferous organic wastewater with high concentration treatment zero draining is realized, is solved existing
Have in technology, solves the problems, such as that operating cost is high in the prior art, processing is halfway, salt content 25wt% or more can be handled
High-COD waste water with high salt；
2) the tubular type free-radical oxidation that the present invention designs handles the integral process of the high COD industrial wastewater of high salinity, realizes
Heat energy self-supporting in system may be used also in addition to maintenance wet type reaction is from the mount of using heat using the heat generated in wet type reaction process
The heating to evaporator is realized in the form of rich producing steam, has saved the energy；
3) LaMn that the present invention usesxCo1-xO3Type perovskite type catalyst, to the with high salt useless of 10wt%-20wt% or so
The catalytic activity of water is more excellent, and has better stability, and COD removal rate is up to 90% or more, and catalyst can continuous work
300 hours or more.
Detailed description of the invention
Fig. 1 is the integral process process that tubular type free-radical oxidation of the invention handles the high COD industrial wastewater of high salinity
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
[embodiment 1]
As shown in Figure 1, a kind for the treatment of process of used water difficult to degradate with high salt, COD is 100000~200000mg/ in waste water
L, salt content 25wt-35wt%,
The technique includes the following steps:
S1, settling sand removing will be carried out in high salt, high-COD waste water importing waste water buffer pool, isolates the sand of bulky grain
Equal substances, to avoid the sand in sewage to the abrasion of pump, the blocking of pipe network, interference even destroys biochemical treatment process；
S2, using sewage pump by waste water buffer in waste water import evaporator in, utilize wet oxidation reactor generate
Hot steam heats waste water, by evaporation high-salt wastewater is concentrated, the preferred waste water total amount of the evaporation capacity of waste water 15~
35%.Condensed water and concentrate are obtained simultaneously, concentrate is cooled down, to make soluble salts substances knot in high-salt wastewater
Crystalline substance is separated, and crystallization salt compounds and crystalline mother solution is obtained by filtration；
S3, crystalline mother solution is added in water distributing trough, waste water salinity detector, and waste water salinity measurement is equipped in distribution reservoir
Device is connected with microcomputer controller, is controlled using microcomputer controller and condensation water quantity is added.Using cold in evaporator
Salinity in water distributing trough is adjusted between 10wt%-15wt% by condensate.
S4, the sewage in water distributing trough is imported into wet oxidation reactor, carries out wet oxidation at a certain temperature, given up
Larger molecular organics in water are by strong oxidizer oxygenolysis, and double bond fracture in organic constitution is oxidized to small by macromolecular
Molecule, small molecule are further oxidized to carbon dioxide and water, greatly improve COD sharp fall BOD/COD value；Wet oxidation
Reactor is free-radical generator, and composite catalyst is mounted in free-radical generator；It is further preferred that the freedom
Base generator includes pressure-air feeding device, and the pressure-air feeding device includes air compressor machine, high-pressure buffering pot and sky
Air-flow meter.The composite catalyst is LaMnxCo1-xO3 perovskite type catalyst, and wherein the range of x value is x=0.01
~0.2；
S4, it is importing directly into microbial degradation pond from the waste water that wet oxidation reactor excludes and carries out microbial degradation；
S5, degradation solution import reverse osmosis membrane processing device and carry out extracting rate, reverse osmosis appears laggard after the filtering of biological carbon filter bed
Guild uses, and reverse osmosis concentrated water with high salt enters low-temperature evaporation crystallization, and the Nacl of generation can be recycled.The material of reverse osmosis membrane
For for cellulose acetate, polyamide, polyimides etc., operating pressure is preferably 1.5-2.5Mpa.
Using integral process of the invention, high saliferous organic wastewater with high concentration treatment zero draining is realized, is solved existing
In technology, solves the problems, such as that operating cost is high in the prior art, processing is halfway, the height of salt content 25wt% or more can be handled
Salt high-COD waste water；Tubular type free-radical oxidation handles the integral process of the high COD industrial wastewater of high salinity, the heat in realization system
Can be self-supporting, it can be with rich producing steam in addition to maintenance wet type reaction is from the mount of using heat using the heat generated in wet type reaction process
Form realize heating to evaporator, saved the energy.
[embodiment 2]
Screening microorganisms: the Facultative Halophiles for having height endurability to salinity are cultivated in screening；By to the micro- life of tradition
Object screening technique is changed, and is configured the culture medium culture microorganism of 10wt%-20wt% salt concentration gradient, is passed through purifies and separates
The Facultative Halophiles for having height endurability to salinity are obtained, the Facultative Halophiles cultivated under high salinity medium have salinity higher resistance to
By property, grown under higher salinity, obtain under high salinity also can normal growth microorganism-Facultative Halophiles.
[embodiment 3]
Prepare composite catalyst:
1) 1mol lanthanum nitrate, 0.2mol manganese nitrate and 0.8mol cobalt nitrate are stoichiometrically weighed, and be dissolved in 5L go from
In sub- water, mixed salt solution is configured, 2.5mol citric acid is then added, stirring to form colloidal sol to being completely dissolved；
2) colloidal sol is dried into moisture at 100 DEG C, be cooled to room temperature, be fully ground 80 meshes；
3) powder after sieving is added in calciner plant, under air atmosphere, carries out microwave heating calcining, the power of microwave
In 1500ww, for heating temperature at 900 DEG C, heating time is to be catalyzed to get with LaMn0.2Co0.8O3 Ca-Ti ore type for 5 minutes
Agent.
[embodiment 3]
The processing of sample sewage:
Sample sewage is chemical plant high-COD waste water with high salt, and COD is 100000~200000mg/L in waste water, and salt content is
25wt-35wt%.
Flow processing as shown in Figure 1 loads composite catalyst prepared by embodiment 3, degradation in free-radical generator
The salt tolerant Halophiles that embodiment 2 is screened is inoculated in pond.The water reuse that salt content is 25wt%, 30wt%, 35wt% is implemented
The integrated process of example 1 is handled, and in 8Mpa, initial reaction stage utilizes conduction oil by reactor temperature for the pressure control of free-radical generator
Degree rises to 250 DEG C, stops heating after reacting normal, for subsequent processes without any heating operation, continuous operation 300 is small
When, it tests it and is discharged COD, the results are shown in Table 1,
Table 1
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (10)
1. the integral process that a kind of tubular type free-radical oxidation handles the high COD industrial wastewater of high salinity, which is characterized in that including under
Column step:
S1, settling sand removing will be carried out in high salt, high-COD waste water importing waste water buffer pool, isolates the substances such as the sand of bulky grain,
To avoid the sand in sewage to the abrasion of pump, the blocking of pipe network, interference even destroys biochemical treatment process；
S2, using sewage pump by waste water buffer in waste water import evaporator in, be evaporated-crystallisation by cooling, by evaporation make
High-salt wastewater concentration, while condensed water and concentrate are obtained, concentrate is cooled down, to make soluble-salt in high-salt wastewater
Substance Crystallization Separation comes out, and crystallization salt compounds and crystalline mother solution is obtained by filtration；
S3, crystalline mother solution is added in water distributing trough, is adjusted to the salinity in water distributing trough using the condensed water in evaporator
Between 10wt%-15wt%；
S4, the sewage in water distributing trough is imported into wet oxidation reactor, carries out wet oxidation at a certain temperature, in waste water
Larger molecular organics by strong oxidizer oxygenolysis, double bond fracture in organic constitution is oxidized to small molecule by macromolecular,
Small molecule is further oxidized to carbon dioxide and water, greatly improves COD sharp fall BOD/COD value；
S4, it is importing directly into microbial degradation pond from the waste water that wet oxidation reactor excludes and carries out microbial degradation；
S5, degradation solution import reverse osmosis membrane processing device and carry out extracting rate, reverse osmosis appears laggard guild after the filtering of biological carbon filter bed
With reverse osmosis concentrated water with high salt enters low-temperature evaporation crystallization, and the Nacl of generation can be recycled.
2. tubular type free-radical oxidation according to claim 1 handles the integral process of the high COD industrial wastewater of high salinity,
It is characterized in that: wet oxidation reactor of the heat source in step S4 in evaporator in step S2.
3. tubular type free-radical oxidation according to claim 1 handles the integral process of the high COD industrial wastewater of high salinity,
It is characterized in that: the 15~35% of the preferred waste water total amount of the evaporation capacity of the waste water in step S2.
4. tubular type free-radical oxidation according to claim 1 handles the integral process of the high COD industrial wastewater of high salinity,
It is characterized in that: being equipped with waste water salinity detector, and waste water salinity detector and microcomputer in the distribution reservoir in step S3
Controller is connected, and is controlled using microcomputer controller and condensation water quantity is added.
5. tubular type free-radical oxidation according to claim 1 handles the integral process of the high COD industrial wastewater of high salinity,
Be characterized in that: wet oxidation reactor is free-radical generator in step S4, and composite catalyzing is mounted in free-radical generator
Agent.
6. tubular type free-radical oxidation according to claim 5 handles the integral process of the high COD industrial wastewater of high salinity,
Be characterized in that: the free-radical generator includes pressure-air feeding device, and the pressure-air feeding device includes pneumatics
Machine, high-pressure buffering pot and air flow meter.
7. tubular type free-radical oxidation according to claim 5 handles the integral process of the high COD industrial wastewater of high salinity,
Be characterized in that: the composite catalyst is LaMnxCo1-xO3 perovskite type catalyst, and wherein the range of x value is x=0.01
~0.2.
8. tubular type free-radical oxidation according to claim 7 handles the integral process of the high COD industrial wastewater of high salinity,
Be characterized in that: the preparation method of the composite catalyst includes the following steps:
1) soluble-salt of the soluble-salt of lanthanum, the soluble-salt of manganese and cobalt is stoichiometrically weighed, and is dissolved in a certain amount of
In deionized water, mixed salt solution is configured, a certain amount of citric acid is then added, stirring to form colloidal sol to being completely dissolved；
2) colloidal sol is dried into moisture, be cooled to room temperature, be fully ground sieving；
3) powder after sieving is added in calciner plant, under air atmosphere, carries out microwave heating calcining to get having
LaMnxCo1-xO3 type perovskite catalyst.
9. tubular type free-radical oxidation according to claim 1 handles the integral process of the high COD industrial wastewater of high salinity,
Be characterized in that: the salt tolerant Halophiles in step S5 be 10-15wt% using concentration high-salt wastewater screening cultivate have
The Facultative Halophiles of height endurability.
10. tubular type free-radical oxidation according to claim 1 handles the integral process of the high COD industrial wastewater of high salinity,
It is characterized by: the material of reverse osmosis membrane is cellulose acetate, polyamide, polyimides etc. in step S5, operating pressure is excellent
It is selected as 1.5-2.5Mpa.
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