CN105330102B - A kind of production technology of improved DSD acid - Google Patents
A kind of production technology of improved DSD acid Download PDFInfo
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Abstract
The invention discloses a kind of production technology of improved DSD acid, including oxidative condensation and acid out step, further include：Step 1, DSD acid oxidative condensation waste water and/or acid out waste water are pre-processed, obtains brackish water, at least one of optional following processing mode is pre-processed：1 a of mode, is filtered after neutralization precipitation；1 b of mode, light electrolysis and filtering；1 c of mode, Fenton oxidation；1 d of mode, flocculation and filtering；1 e of mode, wet oxidation；1 f of mode, absorption；Step 2, brackish water is handled using bipolar membrane electrodialysis, obtains acid solution and alkaline solution；Step 3, to step 1 and/or acid out step, alkaline solution is recycled to step 1 and/or oxidative condensation step for acid solution reuse.Bipolar membrane electrodialysis technology is incorporated into DSD acid technique by the present invention, has not only solved the processing of waste water, but also reduce the input cost of soda acid.
Description
Technical field
The present invention relates to DSD acid production technical field, and in particular to a kind of production technology of improved DSD acid.
Background technology
4,4- diaminobenzil -2,2 disulfonic acid, abbreviation DSD acid (4,4 '-Diaminostilbene-2,2 '
DisulphonicAcid), light yellow paste or powder, are dissolved in ethanol and ether, not soluble in water, are soluble in alkaline solution, and
And red material is easily oxidized in alkaline solution.DSD acid is a kind of important dyestuff intermediate, can be used as Material synthesis one
Serial direct dyes, acid dyes and reactive dye.
At present, the synthesis route of domestic each manufacturing enterprise is that the sulfonated generation para-nitrotoluene of para-nitrotoluene is adjacent
Sulfonic acid (abbreviation NTS acid), oxidized generation 4,4'- dinitrostilbenes -2,2'- disulfonic acid (abbreviation in alkaline aqueous medium
Dinitrostilbene acid or DNS acid), DSD acid most is made through reducing afterwards.The waste water discharged in production process mainly has two parts：A part
It is filtrate caused by oxidative condensation；Another part is the filtrate for reducing workshop section.
The water of DSD acid production waste water is big, and with the spy such as COD high, colourity high, salinity high, B/C is low, pH is low, strong toxicity
Point, is one of very big wastewater from chemical industry of difficulty of governance.DSD acid production waste water main component is band nitro, amino and sulfonic
Aromatic organic compounds, its COD are 20000~25000mg/L, and salinity is 6%~8%, and colourity is 50000 times, and B/C values are only
0.03 or so, belong to the waste water of the extremely difficult degraded of biology.The method of processing DSD acid waste water mainly has at present：Complexing abstraction, resin
Absorption method, chemical oxidization method, micro-electrolysis method, photocatalysis, lotion membrane separation process, resource technology based on multiple-effect evaporation etc..
Sulfate containing high concentration in DSD acid production waste water, has and recycles value well.Publication No.
The patent of invention document of CN102295393A discloses a kind of DSD acid production wastewater treatment technique, using resin adsorption method, to de-
Attached organic matter has carried out resource reclaim, but fails to utilize inorganic salts, while processing cost is higher.
Bipolar Membrane is a kind of new ion-exchange composite membranes, under DC electric field effect, Bipolar Membrane can by hydrolytic dissociation,
Film both sides respectively obtain hydrogen ion and hydroxide ion.Bipolar membrane electrodialysis technology utilizes this feature, by Bipolar Membrane and commonly
Electrodialysis is combined, and the salt in aqueous solution is converted into corresponding bronsted lowry acids and bases bronsted lowry in the case where not being introduced into new component.The technology can
To be widely used in the fields such as food processing, chemical industry synthesis and environmental protection, due to its technical advance, Economic competitive and ring
Border friendly, bipolar membrane electrodialysis technology are known as a kind of sustainable development technology.
The content of the invention
The present invention provides a kind of production technology of improved DSD acid, and the waste water produced in DSD acid production technology is carried out
Pretreatment, to reduce the organic matter in waste water, subsequently into bipolar membrane electrodialysis process, restored acid and the recyclable profit of alkali
With.
A kind of production technology of improved DSD acid, including oxidative condensation and acid out step, further include：
Step 1, DSD acid oxidative condensation waste water and/or acid out waste water are pre-processed, obtains brackish water, pretreatment is appointed
At least one of following processing mode is selected to carry out：
Mode 1-a, is filtered after neutralization precipitation；
Mode 1-b, light electrolysis and filtering：In the case where pH is 2~5 acid condition, treats treatment fluid and carry out light electrolysis, then
Filtering；
Mode 1-c, Fenton oxidation：In the case where pH is 2~5 acid condition, at 40~60 DEG C, added into pending liquid
Molysite and/or ferrous salt, hydrogen peroxide, carry out Fenton oxidation；
Mode 1-d, flocculation and filtering：Flocculant is added into pending liquid, then adjusts pH to 8~10, flocculation finishes
After filtered；
Mode 1-e, wet oxidation：Pending liquid carries out wet oxidation under conditions of 100~300 DEG C, 0.5~10MPa；
Mode 1-f, absorption：Adsorbent is added into pending liquid, is filtered after stirring and adsorbing；
Step 2, brackish water is handled using bipolar membrane electrodialysis, obtains acid solution and alkaline solution；
Step 3, to step 1 and/or acid out step, alkaline solution is recycled to step 1 and/or oxidation contracting for acid solution reuse
Close step.
The preprocessing process purpose that step 1 carries out is, the organic impurities in waste water is removed, it is relatively easy to obtain component
Brackish water.
DSD acid waste water (i.e. DSD acid oxidative condensation waste water and/or acid out waste water) is after pretreatment, organic impurities and color
Degree is basic to be removed, and obtains cleaner brine, and the COD and colourity of brine are relatively low, will not be blocked Bipolar Membrane or be produced swelling to film
Effect.Bronsted lowry acids and bases bronsted lowry, and the hardly water of saliferous are recovered to using Bipolar Membrane.The water of bronsted lowry acids and bases bronsted lowry reuse, hardly saliferous can be done
Technique moisturizing, wash water directly carry out biochemical treatment.
Mode 1-a~mode 1-f is applied in combination and is pre-processed, and can reach good pretreating effect.
In mode 1-a, neutralization precipitation refers to adjust DSD acid oxidative condensation waste water and/or acid out waste water to alkalescence, precipitation
Remove the foreign ion in waste water.
Preferably, in mode 1-a, the pH of waste water is adjusted to 8-10.
Preferably, the light electrolysis in mode 1-b：On the basis of the quality of pending liquid, added into pending liquid micro-
Reagent is electrolysed, the wherein dosage of iron is 0.5~4%, and the mass ratio of iron and carbon is 2~20:1, carry out light electrolysis；Or to treating
The volume ratio of addition iron carbon reagent in treatment fluid, 1~4h of aeration reaction, iron carbon reagent and pending liquid is 1:2~9.
Further preferably, the light electrolysis in mode 1-b：On the basis of the quality of pending liquid, into pending liquid plus 0.5~
The mass ratio of 2% iron and carbon, iron and carbon is 5~10:1, carry out light electrolysis.
In mode 1-b, through galvanic effect following electrode reaction occurs for iron carbon in acid condition：
Anode (Fe):Fe-2e→Fe2+；E θ=- 0.44V
Cathode (C):2H++2e→2[H]→H2；E θ=0V
In reactor, the iron of low potential and the carbon of high potential produce potential difference in waste water system, have certain electric conductivity
Waste water serve as electrolyte, form countless primary batteries, electrochemical reaction occur.Newly generated Fe during anode reaction2+With
Atom H is respectively provided with high chemism, can change the structure and characteristic of useless Organic substance in water；Product during cathode reaction, have
The reduzate of machine thing also all has higher chemism, and the Fe in water outlet3+It can separate out as ferric hydroxide, hydrogen
Iron oxide can adsorb, agglomerate water pollutant, so as to strengthen water treatment effect.
The light electrolysis time in mode 1-b makes choice as needed, it is preferable that the light electrolysis time is 1~6h.Whole
In microelectrolysis process, the pH value of maintenance system is constant.Further preferably, the light electrolysis time is 2~4h.
Preferably, mode 1-c, on the basis of the quality of pending liquid, 0.5~5% iron is added into pending liquid
Salt and/or ferrous salt (total addition of molysite and/or ferrous salt is 0.5~5%), and 0.5~5% hydrogen peroxide, dioxygen
The mass fraction of water is 27~30%, carries out Fenton oxidation.
Molysite and ferrous salt use water soluble salt, for example, molysite generally use ferric sulfate, iron chloride, ferrous salt are usually adopted
With ferrous sulfate, frerrous chloride.
In mode 1-c, Fenton reaction principles are as follows：
Fe2++H2O2→Fe3++OH-+·OH (1)
Fe3++H2O2→Fe2++HO2·+H+ (2)
Fe2++·OH→Fe3++OH- (3)
Fe3++HO2·→Fe2++O2+H+ (4)
·OH+H2O2→H2O+HO2· (5)
Fe2++HO2·→Fe3++HO2 - (6)
RH+·OH→R·+H2O (7)
R·+Fe3+→R++Fe2+ (8)
R·+H2O2→OH++·OH (9)
The reaction of whole system is sufficiently complex, its key is to pass through Fe2+Or Fe3+Play excitation and transmission in the reaction,
And H2O2Then play oxidation, hydroxyl radical free radical OH of the generation with extremely strong oxidability, so that organic in oxidized waste water
Thing.
Carry out continuing stirring during Fenton oxidation, the Fenton oxidation time is 1~2h, Fenton oxidation process
In need to add hydrogen peroxide, while add Fe2+、Fe3+At least one of.
Further preferably, mode 1-c, on the basis of the quality of pending liquid, 0.5~4% is added into pending liquid
Molysite and/or ferrous salt, and 0.5~2% hydrogen peroxide, the mass fraction of hydrogen peroxide is 27~30%, carries out Fenton oxygen
Change.
Preferably, the flocculation in mode 1-d, after adding flocculant into pending liquid, add polyacrylamide and/
Or adsorbent, pH to 8~10 is then adjusted, is flocculated.Persistently stirred in flocculation process, flocculation time is 30~60min.
Preferably, the flocculant is FeSO4·7H2O, polyaluminium sulfate, frerrous chloride, aluminium polychloride, polymerised sulphur
One or more in sour ferro-aluminum, poly-ferric chloride.
On the basis of the quality of pending liquid, the addition of flocculant is 0.2-4%, and the addition of polyacrylamide is
0.0001~0.005%, the addition of adsorbent is 0.02~0.5%.Further preferably, the addition of flocculant is 0.2-
2%, the addition of polyacrylamide is 0.0001~0.001%, and the addition of adsorbent is 0.1~0.5%.
Preferably, in mode 1-e, the condition of wet oxidation is 150~250 DEG C, pressure 1-6MPa.It is further excellent
Select, in mode 1-e, the condition of wet oxidation is 180~240 DEG C, pressure 2-6MPa.
Preferably, in mode 1-f, adsorbent is activated carbon, the one or more in diatomite, with the matter of pending liquid
On the basis of amount, the dosage of adsorbent is 0.02~1%.
Preferably, in mode 1-f, adsorbent is active carbon adsorption column, activated coke, the one or more of molecular sieve.Treat
The volume ratio for the treatment of fluid and adsorbent is 1~200:1.Further preferably, the volume ratio of pending liquid and adsorbent is 20~150:1.
In order to obtain more preferable pretreating effect, clean brackish water is obtained, various pretreatment modes are combined, it is excellent
Selection of land, is pre-processed using following either type：
Mode A, successively ways of carrying out 1-b, mode 1-d；
Mode B, successively ways of carrying out 1-e, mode 1-a, mode 1-f；
Mode C, successively ways of carrying out 1-b, mode 1-e, mode 1-d, mode 1-f；
Mode D, successively ways of carrying out 1-b, mode 1-c, mode 1-d, mode 1-f；
Mode E, successively ways of carrying out 1-e, mode 1-c, mode 1-d, mode 1-f.
Further preferably, mode A is as follows：
Mode 1-b, light electrolysis and filtering：In the case where pH is 2~5 acid condition, in DSD acid oxidative condensation waste water and/or
Light electrolysis reagent is added in acid out waste water, stirring 2~6h of reaction, filters, obtain filtrate I after reaction；
Mode 1-d, flocculation and filtering：Flocculant is added in filtrate I, then adjusts pH to 8~10, flocculation finishes laggard
Row filtering.
Mode B is as follows：
Mode 1-e, wet oxidation：DSD acid oxidative condensation waste water and/or acid out waste water 100~300 DEG C, 0.5~
Wet oxidation is carried out under conditions of 10MPa；
Mode 1-a, filters after neutralization precipitation, the pH of wet oxidation treatment fluid is adjusted to 8~10, filtrate is obtained by filtration
II；
Mode 1-f, absorption：Adsorbent, agitation and filtration are added into filtrate II.
Mode C is as follows：
Mode 1-b, light electrolysis and filtering：In the case where pH is 2~5 acid condition, in DSD acid oxidative condensation waste water and/or
Light electrolysis reagent is added in acid out waste water, 2~6h is reacted, is then filtered, obtain filtrate II I；
Mode 1-e, wet oxidation：Filtrate II I carries out wet oxidation under conditions of 100~300 DEG C, 0.5~10MPa；
Mode 1-d, flocculation and filtering：Flocculant is added into wet oxidation product, then adjusts pH to 8~10, stirring
Flocculate 30~60min, is filtered after flocculation, obtains filtrate IV；
Mode 1-f, absorption：Adsorbent, agitation and filtration are added into filtrate IV.
Mode D is as follows：
Mode 1-b, light electrolysis and filtering：In the case where pH is 2~5 acid condition, DSD acid oxidative condensation waste water and/or acid
Analyse and light electrolysis reagent is added in waste water, react 2~6h, then filtered, obtain filtrate V；
Mode 1-c, Fenton oxidation：PH be 2~5 acid condition under, at 40~60 DEG C, using the quality of filtrate V as
Benchmark, 0.5~4% molysite and/or ferrous salt is added into filtrate V, 0.5~2% hydrogen peroxide, stirring 1~2h of reaction, obtains
To filtrate VI；
Mode 1-d, flocculation and filtering：Flocculant is added into filtrate VI, then adjusting pH to 8~9, stirring flocculation 30~
60min, is then filtered, and obtains filtrate VII；
Mode 1-f, absorption：Adsorbent, agitation and filtration are added into filtrate VII.
Mode E is as follows：
Mode 1-e, wet oxidation：DSD acid oxidative condensation waste water and/or acid out waste water 100~300 DEG C, 0.5~
Wet oxidation is carried out under conditions of 10MPa；
Mode 1-c, Fenton oxidation：In the case where pH is 2~5 acid condition, at 40~60 DEG C, with wet oxidation treatment fluid
Quality on the basis of, 0.5~5% molysite and/or ferrous salt, 0.5~5% hydrogen peroxide are added into wet oxidation treatment fluid, is stirred
1~2h of reaction is mixed, obtains reaction solution；
Mode 1-d, flocculation and filtering：Flocculant is added into reaction solution, then adjusting pH to 8~9, stirring flocculation 30~
60min, is filtered after flocculation, obtains filtrate VIII；
Mode 1-f, absorption：Adsorbent, stirring 30~90min of reaction, filtering are added into wet oxidation product.
In step (2), reaction when bipolar membrane electrodialysis dissociates water is：H2O→H++OH-。
Aqueous sodium persulfate solution is passed through in the compartment being made of anion-exchange membrane and cation-exchange membrane, is made in DC electric field
Under, Na+The OH of water generation is dissociated by cation-exchange membrane and Bipolar Membrane-Generation NaOH is combined in alkali room；SO4 2-By the moon from
The H that proton exchange is produced with Bipolar Membrane dissociation water+Generation H is combined in sour room2SO4。
Electrodialysis concentration is carried out to brackish water preferably, further including, the brine after concentration is carried out at bipolar membrane electrodialysis
Reason, it is 0.1~5% conducting solution as pole liquid that electrodialysis, which uses salt content, and current density is 50~500A/m2。
When carrying out electrodialysis to brackish water, using heterogeneous membrane or half homogeneous membrane, the brackish water that pretreatment is finished
The freshwater room of electrodialysis system is passed through, into the low water of not saliferous or salt content in concentrated water room；Or dense room and light room are all into pre- place
Manage obtained brackish water.After electrodialysis, obtained concentrated water is the salting liquid after concentrating, and obtained fresh water and next group are pre-
The brackish water mixing obtained after processing carries out electrodialysis again.Salting liquid after the concentration obtained after electrodialysis process carries out bipolar
Membrane electrodialysis processing.
Preferably, the inorganic salts in conducting solution are sodium sulphate, potassium sulfate, sodium chloride, one kind in ammonium sulfate or several
Kind.Further preferably, inorganic salts are the one or more in sodium sulphate, potassium sulfate.
Preferably, when step 2 carries out bipolar membrane electrodialysis processing, ruthenium is applied as electrode, current density 100 using titanium
~700A/m2。
Further preferably, when step 2 carries out bipolar membrane electrodialysis processing, apply ruthenium using titanium is as electrode, current density
200~600A/m2。
During bipolar membrane electrodialysis, it is 0.1~5% inorganic salt solution as pole liquid to use salt content, dilute after processing
Salt Water circulation is to electrodialysis step.
After running a period of time, the hydrochloric acid solution that use quality fraction is 2~5% cleans bipolar membranous system.
Compared with the prior art, the present invention has the following advantages：
Bipolar membrane electrodialysis technology is incorporated into DSD acid technique, the waste water that can be produced to technique is handled, at the same time
Obtained acid and alkali is back in technique again, has not only solved the process problem of waste water, but also can reduce the input cost of soda acid.This hair
Bright technological process is succinct, easy to operate, mild condition, and salt while handling waste water in energy recycling waste water, is realized clear
Clean production.
Brief description of the drawings
Fig. 1 is the production technological process of the improved DSD acid of the present invention.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples, it should be pointed out that reality as described below
Apply example to be intended to be easy to the understanding of the present invention, without playing any restriction effect.
If being not particularly limited in the present invention to temperature, carry out at room temperature.
The technological process of the present invention is as shown in Figure 1.
Embodiment 1
DSD acid produces waste water, and pH 3.6, COD are about 23440mg/L, and sulfur acid sodium 7.1% is (using wastewater quality as base
It is accurate).
(1) pre-process：
(1-a) is filtered：Mother liquor waste water filters, and obtains filtrate I；
(1-b) light electrolysis：The pH to 3 of filtrate I is adjusted, successively adds 0.2% activated carbon and 2% iron powder (with the matter of filtrate I
On the basis of amount), stirring reaction 4h, maintenance system pH is constant all the time, filters to get filtrate II after reaction；
(1-c) Fenton oxidation：Filtrate II is adjusted into pH to 3, and heats and keeps the temperature to 45 DEG C, adds 1% (with filtrate II
Quality on the basis of) hydrogen peroxide (mass fraction 30%), stirring reaction 1h, obtain reaction solution III；
(1-d) flocculates：The pH to 8~9 of reaction solution III is adjusted, it is useless to add 0.2% (on the basis of the quality of reaction solution III)
Activated carbon drainage, stirring flocculation 30min, filtering, obtains filtrate IV；
(1-e) is adsorbed：0.2% activated carbon (on the basis of the quality of filtrate IV) is added to filtrate IV, stirring, filtering to filter
Liquid V, the COD of filtrate V is 745mg/L；
(1-f) is concentrated：The diaphragm that electrodialysis uses is heterogeneous membrane, use mass fraction for 1% aqueous sodium persulfate solution
For pole liquid, current density 200A/m2, filtrate V is passed through to the freshwater room of electric osmose system, salt-free clean water is passed through electricity
The concentrated water room of dialysis, obtained concentrated water are the salting liquid after concentrating, and obtained fresh water is mixed with pretreated brackish water again
Pass through electrodialysis；
(2) relieving haperacidity alkali：Salting liquid after the concentration that step (1) obtains is passed through the salt room of bipolar membrane electrodialysis device, output
Bronsted lowry acids and bases bronsted lowry.Titanium is used to apply ruthenium as electrode in bipolar membranous system, diaphragm is homogeneous membrane, initial feed liquid room, sour room and alkali room body
Product is than being 2：1：1, it for 3% aqueous sodium persulfate solution is pole liquid to use mass fraction, current density 450A/m2, after processing
Weak brine be recycled to electrodialysis system concentration, it is 10% to obtain NaOH aqueous solutions that mass fraction is 8% and mass fraction
H2SO4Solution.
(3) soda acid reuse：Obtained H2SO4Solution is back to step (1) and acid out step, NaOH solution are back to step
(1) and oxidative condensation step.
Embodiment 2
DSD acid produces waste water, and pH 3.6, COD are about 23440mg/L, and sulfur acid sodium 7.1% is (using wastewater quality as base
It is accurate).
(1) pre-process：
(1-a) is filtered：Mother liquor waste water filters to get filtrate I；
(1-b) light electrolysis：The pH to 3 of filtrate I is adjusted, successively adds 0.2% activated carbon and 2% iron powder, 4h is reacted in stirring,
All the time maintenance system pH is constant, filters to get filtrate II after reaction；
(1-c) flocculates：The pH to 8~9 of reaction solution II is adjusted, adds 0.1% waste active carbon drainage, stirs flocculation 30min,
Filtering, obtains filtrate III；
(1-d) is adsorbed：0.1% activated carbon is added to filtrate III, stirring filters to get filtrate IV, and the COD of filtrate IV is
934mg/L；
(1-e) is concentrated：The diaphragm that electrodialysis uses is heterogeneous membrane, uses 1% aqueous sodium persulfate solution close for pole liquid, electric current
Spend for 400A/m2, freshwater room and the concentrated water room of electrodialysis plant obtained filtrate IV will be pre-processed are passed through, obtained concentrated water is
Salting liquid after concentration, obtained fresh water is mixed with pretreated filtrate IV again passes through electrodialysis；
(2) relieving haperacidity alkali：Salting liquid after the concentration that step (1) obtains is passed through the salt room of bipolar membrane electrodialysis device, output
Bronsted lowry acids and bases bronsted lowry.Titanium is used to apply ruthenium as electrode in bipolar membranous system, diaphragm is homogeneous membrane, initial feed liquid room and sour room, alkali room body
Product is than being 2：1：1, it for 1% aqueous sodium persulfate solution is pole liquid to use mass fraction, current density 250A/m2, after processing
Weak brine is recycled to electrodialysis system concentration, obtains that mass fraction is 8.5%NaOH aqueous solutions and mass fraction is 9.5%
H2SO4Solution.
(3) soda acid reuse：Obtained H2SO4Solution is back to step (1) and/or acid out step, and NaOH aqueous solutions are back to
Step (1) and/or oxidative condensation step.
Embodiment 3
DSD acid produces waste water, and pH 3.6, COD are about 23440mg/L, and sulfur acid sodium 7.1% is (using wastewater quality as base
It is accurate).
(1) pre-process：
(1-a) neutralization precipitation filters：Water reuse NaOH aqueous solutions are neutralized to 9, and filtering, obtains filtrate I；
(1-b) wet oxidation：For filtrate I under conditions of 260 DEG C, 7MPa, blowing air oxidation, obtains treatment fluid II；
(1-c) is adsorbed：0.2% diatomite (on the basis of II mass for the treatment of fluid) is added to treatment fluid II, stirring, is filtered
Filtrate III, the COD of filtrate III is 1520mg/L；
(1-d) is concentrated：The diaphragm that electrodialysis uses is heterogeneous membrane, uses the mass fraction to be for 1% sodium-chloride water solution
Pole liquid, current density 300A/m2, the filtrate III that pretreatment obtains is passed through to freshwater room and the concentrated water room of electrodialysis plant, is obtained
The concentrated water arrived is the salting liquid after concentrating, and obtained fresh water is mixed with pretreated filtrate III again passes through electrodialysis；
(2) relieving haperacidity alkali：Salting liquid after the concentration that step (1) obtains is passed through the salt room of bipolar membrane electrodialysis device.It is bipolar
Titanium is used to apply ruthenium as electrode in membranous system, diaphragm is homogeneous membrane, and it for 2% sodium-chloride water solution is pole to use mass fraction
Liquid, current density 400A/m2, the weak brine after processing be recycled to electrodialysis system concentration, obtaining mass fraction is
7.5%NaOH solution and mass fraction are 9%H2SO4Solution.
(3) soda acid reuse：Obtained H2SO4Solution is back to acid out step, NaOH aqueous solutions be back to step (1) and/or
Oxidative condensation step.
Embodiment 4
Wastewater treatment method described in embodiment 3, other steps are constant, and pretreatment carries out by the following method：
(1-a) light electrolysis：Iron carbon reagent is added into waste water, it is 1 to keep the volume ratio of iron carbon reagent and waste water:8, aeration
2h is reacted, maintenance system pH is constant all the time, filters to get filtrate I after reaction；
(1-b) wet oxidation：Filtrate I leads to dioxygen oxidation, obtains treatment fluid II under conditions of 240 DEG C, 4MPa；
(1-c) is adsorbed：0.1% diatomite and 0.2% activated carbon are added (using II mass for the treatment of fluid as base to treatment fluid II
It is accurate), stirring filters to get filtrate III, and the COD of filtrate III is 820mg/L；
(1-d) is concentrated：The diaphragm that electrodialysis uses is heterogeneous membrane, uses the mass fraction to be for 1% aqueous sodium persulfate solution
Pole liquid, current density 200A/m2, the filtrate III that pretreatment obtains is passed through to freshwater room and the concentrated water room of electrodialysis plant, is obtained
The concentrated water arrived is the salting liquid after concentrating, and obtained fresh water is mixed with pretreated filtrate III again passes through electrodialysis.
Embodiment 5
DSD acid produces waste water, and pH 3.6, COD are about 15090mg/L, and sulfur acid sodium 3.1% is (using wastewater quality as base
It is accurate).
(1-a) light electrolysis：Iron carbon reagent is added into waste water, it is 1 to keep the volume ratio of iron carbon reagent and waste water:2, aeration
4h is reacted, maintenance system pH is 3 all the time, and standing separation, obtains clear liquid I after reaction；
(1-b) flocculates：Calcium oxide is added into clear liquid I, it is 8 to adjust pH, and after stirring flocculation 1h, filtering, obtains filtrate II,
The COD for measuring filtrate II is 3090mg/L；On the basis of the quality of filtrate II, then 0.2% polyaluminium is added into filtrate II
Aluminium and 0.0002%PAM and 0.05% activated carbon, 0.2% diatomite, stirring flocculation 1h, are obtained by filtration filtrate III, measure its COD
About 1021mg/L.
(1-d) is concentrated：The diaphragm that electrodialysis uses is heterogeneous membrane, uses the mass fraction to be for 1% aqueous sodium persulfate solution
Pole liquid, current density 250A/m2, the filtrate III that pretreatment obtains is passed through to freshwater room and the concentrated water room of electrodialysis plant, is obtained
The concentrated water arrived is the salting liquid after concentrating, and obtained fresh water is mixed with pretreated filtrate III again passes through electrodialysis.
Embodiment 6
Wastewater treatment method described in embodiment 3, other steps are constant, and pretreatment carries out by the following method：
(1-b) wet oxidation：0.2% iron filings (on the basis of wastewater quality) are added in waste water, in 240 DEG C, 4MPa, stirring
Under conditions of speed is 400rpm, leads to dioxygen oxidation 2h, obtain treatment fluid I；
(1-c)Fenton：0.1% iron powder (on the basis of the quality for the treatment of fluid I) is added into treatment fluid I, adjusts pH to 2
Left and right, is heated to 50 DEG C, after 0.5h is reacted in stirring, adds 1.5% hydrogen peroxide (on the basis of the quality for the treatment of fluid I) thereto,
After stirring reaction 1h, add alkali to adjust pH to 8.5, filter to get filtrate II after stirring flocculation 0.5h, the COD of filtrate is 420mg/L；
(1-d) is concentrated：The diaphragm that electrodialysis uses is heterogeneous membrane, uses the mass fraction to be for 1% aqueous sodium persulfate solution
Pole liquid, current density 300A/m2, the filtrate II that pretreatment obtains is passed through to freshwater room and the concentrated water room of electrodialysis plant, is obtained
The concentrated water arrived is the salting liquid after concentrating, and obtained fresh water is mixed with pretreated filtrate II again passes through electrodialysis.
Embodiment 7
Improved DSD acid synthesis technique is：
(1) sulfonation：Into the para-nitrotoluene of molten state plus oleum carries out sulfonating reaction, and acid adding quality is to nitro
3.4 times of toluene quality, acid adding process control temp is at 100 ± 15 DEG C.After the completion of acid adding, 100 DEG C are kept the temperature, stirring is reacted, 1h
After measure product without oil bloom, without to nitre taste, terminate sulfonation.It is diluted with water and cools down mistake after reaction product to its acidity is 50%
Filter, obtains sodium p-nitrotoluene-2-sulfonic acid (abbreviation NTS acid) filter cake and spent acid.Spent acid is sold.
(2) aoxidize：The NTS acidleach cake that step (1) obtains is dissolved with manganese sulfate solution and (in manganese sulfate solution, is added
Measure and add 12 times of quality for para-nitrotoluene, manganese sulfate amount for para-nitrotoluene add quality 1.5%), adjusted with liquid caustic soda anti-
System is answered in alkalescence, the stage is warming up to 70 DEG C, and insulation oxidation 1h, insulation is neutralized to neutrality.
(3) saltout：Nacl is added in the reaction solution obtained to step (2), reaction solution pH to 1 is adjusted, saltouts.Cross
Filter obtains 4,4'- dinitrostilbene -2,2'- disulfonic acid (abbreviation dinitrostilbene acid or DNS acid) and oxidized waste water.Measure DNS
Content is 85%.
(4) reduce：By DNS acid with after water (addition is 14 times that para-nitrotoluene adds quality) dissolving, chlorination is added
Ammonium (addition adds 0.1 times of quality for para-nitrotoluene), is reduced with iron powder (addition is equal with para-nitrotoluene quality)
(reduction temperature be 90 DEG C) to stigma it is colourless when, reef knot beam should, reaction solution is neutralized to pH=8 and the powder stirring reaction that takes a policy
0.5h, is filtered to remove iron cement.Filtered after filtrate acid adding acid out, obtain DSD acid and reducing waste water.After DSD acid drying, amino is measured
It is worth for 97%.
(5) wet oxidation：Oxidized waste water (COD 24900mg/L, sodium sulphate content 8%, the pH that step (3) is obtained
4) to adjust pH to 9, it is transferred to after filtering in wet oxidation reaction kettle, is passed through N2Oxygen is passed through in 2 backward kettles of displacement, is adjusted in kettle
Pressure is 4Mpa, and heated waste water is maintained at 230 DEG C, the condition of 4Mpa to 230 DEG C, after aoxidizing 3h, sodium oxide molybdena is hydrogenated with into waste water
Adjust to pH=9, then after being passed through ozone oxidation 2h thereto, add 0.3% activated carbon (on the basis of the quality of oxidized waste water),
Stirring reaction 1h, is obtained by filtration filtrate.Liquor C OD about 230mg/L.
(6) concentrate：Above-mentioned filtrate respectively enters the dense room of electrodialytic membranes system and (electrodialytic membranes is half homogeneous for light room
Film, it for 1% aqueous sodium persulfate solution is pole liquid to use mass fraction, current density 200A/m2), salt content is in dense room water outlet
12%, light room water outlet salt content is 0.7%.
(7) relieving haperacidity alkali：The dense room water outlet of step (5) enters bipolar membranous system, and (Bipolar Membrane diaphragm is half homogeneous membrane, is used
Mass fraction is that 2% aqueous sodium persulfate solution is pole liquid, current density 400A/m2) raw water room, the light room that step (6) obtains
Water inlet of the water outlet as sour room and alkali room.Sour room water outlet is the sulfuric acid solution that mass fraction is 10%, and alkali room water outlet is quality point
Number is 7% sodium hydroxide solution.
(8) wet oxidation：The reducing waste water (COD 30800mg/L, pH 2) that step (4) is obtained is transferred to wet oxidation
In reaction kettle, N is passed through2Oxygen is passed through in 2 backward kettles of displacement, it is 5Mpa to adjust pressure in kettle, and heated waste water is protected to 250 DEG C
To hold 250 DEG C, the condition of 5Mpa, after aoxidizing 3h, be cooled to 55 DEG C, the acid adding into waste water, it is 3.5 to adjust wastewater pH, then to waste water
Add 0.2% FeSO4·7H2The hydrogen peroxide (on the basis of the quality of reducing waste water) of O and 1.5%, after stirring and dissolving, adds
Sodium hydroxide adjusts to pH=10, stirring reaction 1h, the filtrate being obtained by filtration and is warming up to 80 DEG C, is passed through air stripping 2h, add
0.3% activated carbon (on the basis of the quality of reducing waste water), stirring reaction 0.5h, is obtained by filtration filtrate.Liquor C OD about 330mg/
L.Stripping tail gas is absorbed with dilute hydrochloric acid solution, and obtained ammonium chloride solution is concentrated through electrodialysis, continues on for reduction step.Obtain
Filtrate after electrodialysis concentrates, then through bipolar film process, obtain sulfuric acid and sodium hydroxide.
(9) sulfuric acid solution obtained in step (7) and (8) is used to adjust pH in wastewater treatment process, remaining is used as DSD acid
Acid out step, the neutralization acidifying after oxidation step；Sodium hydroxide is used to adjust pH in wastewater treatment process, remaining is used as DSD
The oxidation step of acid.
Claims (6)
1. a kind of production technology of improved DSD acid, including oxidative condensation and acid out step, it is characterised in that further include：
Step 1, DSD acid oxidative condensation waste water and/or acid out waste water are pre-processed, obtain brackish water, pretreatment optionally with
At least one of lower processing mode carries out：
Mode B, carries out successively：
Mode 1-e, wet oxidation：DSD acid oxidative condensation waste water and/or acid out waste water are in 100~300 DEG C, 0.5~10MPa
Under the conditions of carry out wet oxidation；
Mode 1-a, filters after neutralization precipitation, the pH of wet oxidation treatment fluid is adjusted to 8~10, filtrate II is obtained by filtration；
Mode 1-f, absorption：Adsorbent, agitation and filtration are added into filtrate II；
Mode C, carries out successively：
Mode 1-b, light electrolysis and filtering：In the case where pH is 2~5 acid condition, in DSD acid oxidative condensation waste water and/or acid out
Light electrolysis reagent is added in waste water, 2~6h is reacted, is then filtered, obtain filtrate II I；
Mode 1-e, wet oxidation：Filtrate II I carries out wet oxidation under conditions of 100~300 DEG C, 0.5~10MPa；
Mode 1-d, flocculation and filtering：Flocculant is added into wet oxidation product, then adjusts pH to 8~10, stirring flocculation
30~60min, is filtered after flocculation, obtains filtrate IV；
Mode 1-f, absorption：Adsorbent, agitation and filtration are added into filtrate IV；
Mode E, carries out successively：
Mode 1-e, wet oxidation：DSD acid oxidative condensation waste water and/or acid out waste water are in 100~300 DEG C, 0.5~10MPa
Under the conditions of carry out wet oxidation；
Mode 1-c, Fenton oxidation：In the case where pH is 2~5 acid condition, at 40~60 DEG C, with the matter of wet oxidation treatment fluid
On the basis of amount, 0.5~5% molysite and/or ferrous salt, 0.5~5% hydrogen peroxide are added into wet oxidation treatment fluid, stirring is anti-
1~2h is answered, obtains reaction solution；
Mode 1-d, flocculation and filtering：Flocculant is added into reaction solution, then adjusting pH to 8~9, stirring flocculation 30~
60min, is filtered after flocculation, obtains filtrate VIII；
Mode 1-f, absorption：Adsorbent, stirring 30~90min of reaction, filtering are added into filtrate VIII；
Step 2, brackish water is handled using bipolar membrane electrodialysis, obtains acid solution and alkaline solution；Carry out Bipolar Membrane
During electrodialysis process, current density is 100~700A/m2；
Step 3, to step 1 and/or acid out step, alkaline solution is recycled to step 1 and/or oxidative condensation step for acid solution reuse
Suddenly.
2. the production technology of improved DSD acid as claimed in claim 1, it is characterised in that the light electrolysis in mode 1-b：With
On the basis of the quality of pending liquid, into pending liquid add light electrolysis reagent, wherein the dosage of iron be 0.5~4%, iron and
The mass ratio of carbon is 2~20:1, carry out light electrolysis；Or iron carbon reagent, 1~4h of aeration reaction, iron are added into pending liquid
The volume ratio of carbon reagent and pending liquid is 1:2~9.
3. the production technology of improved DSD acid as claimed in claim 1, it is characterised in that mode 1-c, with pending liquid
On the basis of quality, 0.5~5% molysite and/or ferrous salt, and 0.5~5% hydrogen peroxide are added into pending liquid, it is double
The mass fraction of oxygen water is 27-30%, carries out Fenton oxidation.
4. the production technology of improved DSD acid as claimed in claim 1, it is characterised in that the flocculation in mode 1-d, to treating
After adding flocculant in treatment fluid, polyacrylamide and/or adsorbent are added, pH to 8~10 is then adjusted, flocculates.
5. the production technology of improved DSD acid as claimed in claim 1, it is characterised in that in mode 1-f, adsorbent is work
Property charcoal, the one or more in diatomite, on the basis of the quality of pending liquid, the dosage of adsorbent is 0.02~1%.
6. the production technology of improved DSD acid as claimed in claim 1, it is characterised in that further include and electricity is carried out to brackish water
Dialysis concentrates, and brine after concentration carries out bipolar membrane electrodialysis processing, electrodialysis use salt content for 0.1~5% it is conductive molten
For liquid as pole liquid, current density is 50~500A/m2。
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| CN106315936B (en) * | 2016-08-31 | 2020-03-10 | 浙江奇彩环境科技股份有限公司 | Method for treating bromamine acid wastewater |
| CN108793573A (en) * | 2018-06-14 | 2018-11-13 | 浙江奇彩环境科技股份有限公司 | The processing method of pyridine waste water with high salt |
| CN110563217A (en) * | 2019-08-13 | 2019-12-13 | 广东上智环保科技有限公司 | Sewage treatment process and equipment |
| CN112607892A (en) * | 2020-11-09 | 2021-04-06 | 西安重光明宸检测技术有限公司 | Efficient and environment-friendly method for reducing COD (chemical oxygen demand) of sewage |
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