CN108178361A - The reverse osmosis combined treatment process for generating strong brine in a kind of coal chemical industrial waste water reuse - Google Patents
The reverse osmosis combined treatment process for generating strong brine in a kind of coal chemical industrial waste water reuse Download PDFInfo
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- CN108178361A CN108178361A CN201611120857.2A CN201611120857A CN108178361A CN 108178361 A CN108178361 A CN 108178361A CN 201611120857 A CN201611120857 A CN 201611120857A CN 108178361 A CN108178361 A CN 108178361A
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- hydrogen peroxide
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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
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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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The strong brine that the present invention is generated for reverse osmosis units during coal chemical industrial waste water reuse proposes a kind of efficient combined treatment process, belongs to sewage disposal and environment functional material field.Involved treatment process is included except four ammonia unit, catalyzing hydrogen peroxide oxidation unit, condensing crystallizing unit and fresh water reuse unit operating units.The technique will be coupled except ammonia technology with catalytic wet hydrogen peroxide oxidation technology, it can the organic compounds and ammonia nitrogen etc. such as remaining phenols pollution class substance in the strong brine that generates of efficient process reverse osmosis units, ensure that the solid salt generated after concentrated crystallization and evaporation is white, fresh water can reuse.The process efficiency is high, and method is simple and practicable, of low cost, highly practical, and non-secondary pollution, has important science and application value.
Description
Technical field
The present invention relates to the advanced treating groups for the strong brine that reverse osmosis units during a kind of coal chemical industrial waste water reuse generate
Technique is closed, is characterized as by removing ammonia unit, catalytic wet hydrogen peroxide oxidation unit, condensing crystallizing unit and fresh water reuse unit
Four operating unit couplings effectively remove COD and ammonia nitrogen in reverse osmosis generation strong brine, realize effluent reuse and ensure solid
Purity salt belongs to sewage disposal and environment functional material field.
Background technology
Coal chemical industry is translated into gas, liquid, solid fuel simultaneously using coal as raw material, by series of chemical
Produce various chemical product.Since coal is play an important role in Chinese energy produces structure, coal chemical industry becomes China
One of energy development strategy emphasis.In recent years, it is big, generation useless with water consumption with the raising of state sewage emission standard
The coal chemical industry for the features such as water water quality is complicated, intractability is big has become the emphasis of environment protection treating.Seek treatment effect it is more preferable,
The waste water treatment process that technology stability is stronger, operating cost is lower is realized " wastewater zero discharge ", has become Development of Coal Chemical Industry
Self-demand and external requirement.
Typical coal chemical industrial waste water processing usually first passes through the pretreatments such as oil removing, dephenolize, ammonia still process, at secondary biochemical
Reason and three-level advanced treatment process.And it improves producing water water quality, realize that the key link of the effective reuse of coal chemical industrial waste water or discharge exists
In advanced treatment process, including links such as impurity concentration, evaporative crystallizations.Film concentration technique is due to at low cost, scale is big, skill
The advantages that art is ripe, therefore usually as the one preferred technique of coal chemical industry strong brine advanced treating.Wherein, reverse osmosis process processing is useless
Water desalination effect is fabulous, produces relatively low containing COD, salt density in clear water, the clear water rate of recovery generally about 60~80%.However, through
Strong brine salt content after reverse osmosis membrane concentration is typically up to more than 20wt.%, simultaneously containing containing a certain amount of bio-refractory
Nitrogen material and organic matter.It, can not direct emission, effectively place since dope water quality is more complicated, salinity is higher and biodegradability is poor
Reason is also faced with great difficulty.103922549 A of patent CN propose a kind of coal chemical industrial waste water treatment for reuse method and device,
By multinomial wastewater processing technology optimum organization in " pretreatment+biochemistry+advanced treating " technique, but not to reverse osmosis concentrated brine into
Row is further processed.104478173 A of patent CN use " Na-ion exchanger+negative and positive membrane electrodialysis/high pressure reverse osmosis membrane " skill
The strong brine of the reverse osmosis generation of art processing, recycles crystal salt or soda acid, is discharged COD about 60mg/L, ammonia nitrogen about 12mg/L, but exist
The problems such as processing cost is higher, system stability is poor.Country's the sector water consumption is very big at present, therefore builds and be suitable for coal chemical industry
The strong brine of reverse osmosis generation during waste water recycling administer with a whole set of technical matters of reuse, make nitrogen substance and organic matter equal
Reach or be of great significance close to " zero-emission ".
The organic compound that coal chemical industrial waste water contains in the strong brine after reverse-osmosis treated is mostly phenols and condensed ring virtue
The substances such as hydrocarbon.Advanced oxidation processes (AOPs) are one of maximally efficient methods of current degradation of organic substances, have relatively broad reality
It applies on border.Wherein, catalytic wet hydrogen peroxide oxidation method (CWPO) using non-toxic inexpensive H2O2Oxidant is wet instead of being catalyzed
The hyperbaric oxygen or compressed air used in formula air oxidation process (CWAO) can be grasped to avoid the equipment burn into caused by high pressure
Make security problems, while eliminate influence of the gas-liquid mass transferring resistance to reaction rate, accelerate reaction speed, effectively decomposing can
The poor persistent organic pollutants of biochemical.When cannot larger molecular organics exhaustive oxidation be decomposed into CO2And H2During O, also lead to
Small toxicity and the compound of easily biological-degradable can be often translated into.In addition, CWPO can be under low-temperature atmosphere-pressure by H2O2Decompose production
The raw hydroxyl radical free radical (HO) with Strong oxdiative ability, without supplementary means such as electric current, ultraviolet lights, have it is easy to operate, into
The advantages of this is cheap.Salinity is not limited in by water for the use of CWPO technologies, therefore for the middle low concentration organic waste of high salinity
The processing of water has certain application prospect.
The present invention provides a kind of depth of high-efficiency environment friendly for the dense salt waste water of reverse osmosis generation in coal chemical industrial waste water reuse
Processing method is spent, the reuse water quality after reverse osmosis process and solid purity salt have been ensured as key technology.By " ultrafiltration+
It is reverse osmosis " fresh water that generates of technique realizes reuse or discharge, and because the residual pollutants such as COD and ammonia nitrogen make in the strong brine generated
Waste water water quality after solid salts out is not still up to standard.The present invention is further dropped using except ammonia unit with method associated with CWPO technologies
The remaining organic or inorganic pollutant in waste water is solved, improves effluent quality and solid purity salt.In the various of removal nitrogen substance
It is simple and practicable by the breakpoint facture of chlorination in physical chemistry method, it is highly practical, it removes nitrogenous in the strong brine of reverse osmosis generation
It can remove a small amount of organic matter while substance.The catalyst that CWPO technologies use in the present invention has high mechanical strength, thermostabilization
The features such as property and chemical stability are good, under low-temperature atmosphere-pressure can efficient catalytic degrade such waste water, service life is longer, is suitable for
Industrialize prolonged application.Therefore, the present invention selects sodium hypochlorite ammonia elimination process to be combined with CWPO technologies, under mild reaction condition
The ammonia nitrogen and organic matter in waste water are efficiently handled, improves solid purity salt in subsequent processing, there is applied widely, reaction speed
Spend the advantages such as fast, of low cost and secondary pollution is low.The solid salt generated after group technology processing in the present invention is realized back
It receives or landfill, water outlet COD can be controlled in 60mg/L hereinafter, can meet HG/T 3923-2007《Recirculated cooling water recycled water water
Matter standard》Requirement, while there is decoloration, denitrogenation and other effects, after processing can direct reuse in circulation moisturizing.
Invention content
The strong brine that the present invention is generated for reverse osmosis units during coal chemical industrial waste water reuse, overcomes existing processing method
The drawbacks of middle and deficiency, provide a kind of efficiently feasible processing method, that is, couple break point chlorination and catalytic wet hydrogen peroxide
Oxidizing process (CWPO) removes remaining ammonia nitrogen and organic pollution in strong brine successively.This is simple for process, in low-temperature atmosphere-pressure
Under can efficiently improve waste water quality, non-secondary pollution can carry out depth degradation and row up to standard to the strong brine of reverse osmosis generation
It puts.
The present invention provides the concrete schemes of above-mentioned technique：
1. the strong brine processing technology that reverse osmosis units during a kind of coal chemical industrial waste water reuse generate is provided, including removing ammonia
Four unit, catalytic wet hydrogen peroxide oxidation unit, condensing crystallizing unit and fresh water reuse unit operating units.It is described to remove ammonia
Unit includes NaClO basins and pipe-line mixer；NaClO basins and reverse osmosis concentrated brine water and pipe-line mixer water inlet
It is connected；The catalytic wet hydrogen peroxide oxidation unit includes sulfuric acid basin, pH adjusts tank, hydrogen peroxide basin, is catalyzed instead
Answer tower and hydrogen peroxide decomposition tower；The water outlet of ammonia unit and the sulfuric acid basin of removing is connected with pH adjusting tank water inlets；Catalysis
Reaction tower water inlet adjusts tank with the pH respectively and hydrogen peroxide basin is connected, while water outlet and hydrogen peroxide decomposition tower
It is connected；The strong brine condensing crystallizing unit is connected with the outlet of hydrogen peroxide decomposition tower.
2. reverse osmosis units are generated in the combined treatment process of strong brine during coal chemical industrial waste water reuse, the strong brine
It is mixed, is discharged after processing in pH adjusts tank through peracidity through pipe-line mixer with the NaClO solution of NaClO basins output
It adjusts, then is delivered to catalytic wet hydrogen peroxide oxidation unit, and enter after being mixed with the hydrogen peroxide in hydrogen peroxide basin
Catalytic tower bottom；Catalysis reaction water outlet at the top of catalytic tower by entering at the top of hydrogen peroxide decomposition tower, from decomposition tower bottom
Portion is discharged, and fresh water carries out reuse after eventually entering into condensing crystallizing cell processing.
3. coal chemical industrial waste water generates 70%~80% fresh water recoverable after reverse osmosis units are handled, strong brine is generated
Volume fraction be 20%~30%, COD value be 80~200mg/L, ammonia nitrogen value be 20~45mg/L, the ammonia after removing ammonia cell processing
Values of nitrogen might is less than 12mg/L, and COD value of waste water is less than 60mg/L after CWPO process；
4. except a concentration of 10~30wt.%, ClO of NaClO in ammonia unit-/NH4 +(molar ratio)=0.5~3:1.
5. H in the catalytic tower of catalytic wet hydrogen peroxide oxidation unit2O2Addition for theory demands amount 0.5~
3.0 times, 0.5~5.0h of reaction tower air speed-1.Heterogeneous catalysis is loaded in catalytic tower, is loaded in hydrogen peroxide decomposition tower
Manganese sand, method for preparing catalyst and relevant specific contents are the same as patent 201510810646.0.
Beneficial effects of the present invention and advantage are：
The present invention is combined processing reverse osmosis units using economical and efficient, simple and practicable break point chlorination with CWPO technologies
The strong brine difficult to degrade generated, solid purity salt and reuse water quality in effective guarantee subsequent technique.Wherein, CWPO technologies are catalyzed
Using heterogeneous catalysis during oxidized waste water, be not only adapted to the wastewater treatment of wider pH range, at the same loss of active component amount it is small,
Utilization rate is high, the problems such as avoiding the generation of iron cement in homogeneous catalysis；CWPO catalyst is higher and low-cost using activity
Transition metal or rare earth metal, using most common raw material of industry aluminium oxide and activated carbon as carrier, have as active component
There are higher thermal stability and good mechanical strength.The present invention has considered catalyst activity, stability and economy, tool
There is preferable industrial applications prospect.
Description of the drawings
The reverse osmosis advanced treatment process flow chart for generating strong brine during Fig. 1 coal chemical industrial waste water reuses.
Water outlet COD is measured after reverse osmosis generation strong brine processing during Fig. 2 coal chemical industrial waste water reuses.
Specific embodiment
Reverse osmosis units generate the combined treatment process of strong brine, tool during coal chemical industrial waste water reuse of the present invention
Body includes the following steps：Coal chemical industrial waste water is by reverse osmosis units treated strong brine, the NaClO with the output of NaClO basins
Solution is mixed through pipe-line mixer, is discharged after processing and is adjusted, then be delivered to catalytic wet through peracidity in pH adjusts tank
Hydrogen peroxide oxidation unit, and enter catalytic tower bottom after being mixed with the hydrogen peroxide in hydrogen peroxide basin；Catalysis is anti-
It should be discharged by entering at the top of hydrogen peroxide decomposition tower at the top of catalytic tower, from tower bottom water outlet is decomposed, eventually enter into concentration knot
Qualified discharge after brilliant cell processing.
The following example carries out in laboratory, for illustrating strong brine group technology processing method in the present invention.Experiment is adopted
The dense salt waste water generated with reverse osmosis units during coal chemical industrial waste water reuse, water quality index are as follows：COD:100~200mg/L,
Ammonia nitrogen:10~34mg/L, pH:7~9, salinity:3.8%.Strong brine combination process for advanced treatment as shown in Figure 1, including successively
Sequence connection removes ammonia unit, catalytic wet peroxidating deoxidation unit, concentrated water condensing crystallizing unit and fresh water reuse unit.Catalysis
Wet type peroxidating deoxidation unit：Catalytic reactor be upflow fixed bed reactor (internal diameter 21mm, high 170mm), catalyst
(4~10 mesh) loadings：50mL；Method for preparing catalyst is the same as patent 201510810646.0；Except ammonia unit is discharged through peracidity
It adjusts, adds in after a certain amount of hydrogen peroxide mixing through inputting catalytic reactor bottom, LHSV together by metering pump:1h-1；Water outlet
It can white salt processed through Rotary Evaporators evaporation process.
Embodiment 1
(1) except ammonia unit：Influent COD：200mg/L；NH3- N=30mg/L；Through denitrogenation processing, NaClO concentration：
30wt.%, ClO-/NH4 +(molar ratio)=1.5:1；COD=185mg/L after processing, NH3- N=7mg/L；
(2) catalyzing hydrogen peroxide oxidation unit：It is 5 that water inlet adjusts pH value in water storing tank, and is delivered to catalytic tower
Bottom；In catalytic tower catalyst be 3wt.%Fe-0.5wt.%Ce/ modified activated carbons, H2O2(mg/L):COD (mg/L)=
1,300h is run, water outlet COD is about 50mg/L (such as Fig. 2), about 1 times of coloration.
Embodiment 2
(1) except ammonia unit：Influent COD：180mg/L；NH3- N=25mg/L；Through denitrogenation processing, NaClO concentration：
30wt.%, ClO-/NH4 +(molar ratio)=1:1；COD=172mg/L after processing, NH3- N=10mg/L；
(2) catalyzing hydrogen peroxide oxidation unit：It is 5 that water inlet adjusts pH value in water storing tank, and is delivered to catalytic tower
Bottom；In catalytic tower catalyst be 2wt.%Cu-0.5wt.%Ce/ modified activated carbons, H2O2(mg/L):COD (mg/L)=
1.5, LHSV 1h-1；200h is run, water outlet COD is about 55mg/L, about 2 times of coloration.
Embodiment 3：
(1) except ammonia unit：Influent COD：150mg/L；NH3- N=33mg/L；Through denitrogenation processing, NaClO concentration：
30wt.%, ClO-/NH4 +(molar ratio)=1.8:1；COD=144mg/L after processing, NH3- N=8mg/L；
(2) catalyzing hydrogen peroxide oxidation unit：It is 4 that water inlet adjusts pH value in water storing tank, and is delivered to catalytic tower
Bottom；In catalytic tower catalyst be 1.5wt.%Fe-0.5wt.%Ni/ modified activated carbons, H2O2(mg/L):COD(mg/L)
=2, LHSV 0.5h-1；200h is run, water outlet COD is about 60mg/L, about 3 times of coloration.
Embodiment 4：
(1) except ammonia unit：Influent COD：200mg/L；NH3- N=30mg/L；Through denitrogenation processing, NaClO concentration：
30wt.%, ClO-/NH4 +(molar ratio)=2:1；COD=170mg/L after processing, NH3- N=9mg/L；
(2) catalyzing hydrogen peroxide oxidation unit：It is 6 that water inlet adjusts pH value in water storing tank, and is delivered to catalytic tower
Bottom；In catalytic tower catalyst be 2wt.%Fe-1wt.%Cu/ aluminium oxide, H2O2(mg/L):COD (mg/L)=2, LHSV
For 0.5h-1；200h is run, water outlet COD is about 50mg/L, about 2 times of coloration.
Embodiment 5：
(1) except ammonia unit：Influent COD：150mg/L；NH3- N=34mg/L；Through denitrogenation processing, NaClO concentration：
30wt.%, ClO-/NH4 +(molar ratio)=1.5:1；Flow is 18L/h；COD=125mg/L after processing, NH3- N=8mg/L；
(2) catalyzing hydrogen peroxide oxidation unit：It is 4 that water inlet adjusts pH value in water storing tank, and is delivered to catalytic tower
Bottom；In catalytic tower catalyst be 2wt.%Ni-0.3wt.%Ce/ modified activated carbons, H2O2(mg/L):COD (mg/L)=
1.5, LHSV 0.5h-1；200h is run, water outlet COD is about 55mg/L, about 3 times of coloration.
Conclusion：
Group technology according to the present invention is included except ammonia unit, catalyzing hydrogen peroxide oxidation unit, condensing crystallizing unit
And fresh water reuse unit, the drawbacks of overcoming in the existing deep treatment method of coal chemical industrial waste water with insufficient, for coal chemical industrial waste water
The strong brine that reverse osmosis units generate in reuse carries out depth degradation.The technique is by break point chlorination and heterogeneous catalysis wet type mistake
Oxidation hydrogen oxidation technique is combined, and simple and practicable, reaction condition is mild, can effectively remove ammonia nitrogen in waste water and organic matter, Bu Huizao
Into secondary pollution.It is demonstrated experimentally that by modified aluminas/activated-carbon catalyst (see patent 201510810646.0) applied to catalysis
In wet-type peroxide oxidizing technology, can depth degradation reverse osmosis units generate strong brine in organic pollution, COD will be discharged
Be down to 60mg/L hereinafter, and operation 300h after effect can still be held essentially constant, show that the catalyst can be in faintly acid to neutrality
Greater activity and stability are maintained in waste water.Reverse osmosis units generate during a kind of processing coal chemical industry reuse of present invention offer
The efficient feasible group technology of strong brine, using the heterogeneous catalysis that price is less expensive, is easily isolated and recycled in CWPO technologies
Agent can be used under low-temperature atmosphere-pressure, effectively realize the advanced treating that reverse osmosis units generate strong brine, finishing department waste
Zero-emission provides safeguard for effectively operating.
Claims (7)
1. reverse osmosis units generate the combined treatment process of strong brine during a kind of coal chemical industrial waste water reuse, it is characterised in that：
Combined treatment process is included except three ammonia unit, catalytic wet hydrogen peroxide oxidation unit and condensing crystallizing unit operating units.
2. strong brine combined treatment process according to claim 1, it is characterised in that：
The ammonia unit that removes includes NaClO basins and pipe-line mixer；NaClO basins and the strong brine of reverse osmosis generation difference
It is connected with pipe-line mixer water inlet；
The catalytic wet hydrogen peroxide oxidation unit includes sulfuric acid basin, pH adjusts tank, hydrogen peroxide basin, catalytic tower
With hydrogen peroxide decomposition tower；The water outlet of ammonia unit and the sulfuric acid basin of removing is connected with pH adjusting tank water inlets；Catalysis reaction
Tower water inlet adjusts tank with the pH respectively and hydrogen peroxide basin is connected, while water outlet is connected with hydrogen peroxide decomposition tower
It is logical；
The strong brine condensing crystallizing unit is connected with the outlet of hydrogen peroxide decomposition tower.
3. strong brine combined treatment process according to claim 1, it is characterised in that：The strong brine and NaClO basins
The NaClO solution of output is mixed through pipe-line mixer, is discharged after processing and is adjusted, then convey through peracidity in pH adjusts tank
To catalytic wet hydrogen peroxide oxidation unit, and enter catalytic tower bottom after being mixed with the hydrogen peroxide in hydrogen peroxide basin
Portion；Catalysis reaction water outlet is by entering at the top of hydrogen peroxide decomposition tower at the top of catalytic tower, from tower bottom water outlet is decomposed, finally into
Fresh water carries out reuse or discharge after entering condensing crystallizing cell processing.
4. strong brine combined treatment process according to claim 1 or 2, it is characterised in that：Coal chemical industrial waste water reuse process
The strong brine volume fraction that middle reverse osmosis units generate is the 20%~30% of raw water, and COD value is 80~200mg/L, ammonia nitrogen value
For 20~45mg/L, ammonia nitrogen value is less than 12mg/L after removing ammonia cell processing, and COD value of waste water is less than after CWPO process
60mg/L。
5. strong brine combined treatment process according to claim 2, it is characterised in that：Except the concentration of NaClO in ammonia unit
For 10~30wt.%, ClO-/NH4 +(molar ratio)=0.5~3:1.
6. strong brine combined treatment process according to claim 2, it is characterised in that：Catalytic wet hydrogen peroxide oxidation list
H in the catalytic tower of member2O2Addition is 0.5~3.0 times of theoretical requirement, 0.5~5.0h of reaction tower air speed-1；Catalysis
It loading heterogeneous catalysis in reaction tower, loads A/X type heterogeneous catalysis in tower, wherein A is active component, specially Fe,
One or two or more kinds in Ce, Cu, Ni, X are catalyst carrier, specially one kind in activated carbon, aluminium oxide or two kinds with
On；Filling manganese sand in hydrogen peroxide decomposition tower.
7. strong brine combined treatment process according to claim 3, it is characterised in that：Through peracidity tune in pH adjusts tank
PH is saved as 4-7, the mass concentration of sulfuric acid is 10%~50% in sulfuric acid basin.
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Cited By (1)
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| CN114149109A (en) * | 2021-12-03 | 2022-03-08 | 内蒙古科技大学 | Method for purifying slime water by cerium catalysis |
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