CN102417229B - Method for removing azo dye waste water chroma by using hydrogen sulfide waste gas - Google Patents
Method for removing azo dye waste water chroma by using hydrogen sulfide waste gas Download PDFInfo
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- CN102417229B CN102417229B CN 201110324183 CN201110324183A CN102417229B CN 102417229 B CN102417229 B CN 102417229B CN 201110324183 CN201110324183 CN 201110324183 CN 201110324183 A CN201110324183 A CN 201110324183A CN 102417229 B CN102417229 B CN 102417229B
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- waste water
- hydrogen sulfide
- waste
- waste gas
- anthraquinone
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Abstract
The invention provides a method for removing azo dye waste water chroma by using hydrogen sulfide waste gas. According to the method, soluble anthraquinone is added into azo dye waste water, and hydrogen sulfide waste gas contacts and reacts with the azo dye waste water through a certain process so as to remove hydrogen sulfide in waste gas and chroma in waste water synchronously and to obtain elemental sulfur having industrial use simultaneously. The beneficial effects of the invention are as follows: through utilization of hydrogen sulfide waste gas for decoloring, an anaerobic bioprocess or a chemical reducing agent needed in decoloring of dye waste water can be saved, a desulfurizer regeneration process needed in purification of hydrogen sulfide flue gas can be omitted, and the waste is treated with waste, thereby substantially reducing cost for controlling pollution, enabling comprehensive control of waste water and waste gas to be realized and benefiting resource conservation and environmental protection.
Description
Technical field
The present invention relates to a kind for the treatment of process of waste water from dyestuff, particularly a kind of hydrogen sulfide waste gas that adopts belongs to environmental protection technical field to the treatment process of azoic dyestuff molecule decolored degradation in the azo dye wastewater.
Background technology
The waste water from dyestuff complicated component, organic pollutant content height, colourity are dark, alkalescence greatly, wherein contained dyestuff has " three causing property " (i.e. carcinogenic, teratogenesis, mutagenesis) mostly, if will bring serious harm to ecotope without handling direct discharging.The dyestuff that contains one or more azo bond (N=N) in the molecule is called azoic dyestuff, be kind and the maximum class of quantity in the synthetic dyestuff, comprise substantive dyestuff, matching stain, reactive dyestuffs, metallized dye, dispersed dye, cationic dyestuff and the condensation dye etc., account for 70% of whole world DYE PRODUCTION total amount.Also contain structures such as amino, sulfonic group, phenyl ring or naphthalene nucleus in most azoic dyestuff molecules, these structures are given characteristics such as the anti-photodissociation of azoic dyestuff, anti-oxidant, antibiont degraded, and therefore, the processing of azo dye wastewater more and more causes people's attention.
Adopt conventional treatment technology often to be difficult to the effect that reaches desirable.Handle as traditional physico-chemical process and to exist the processing cost height, treatment capacity is little and shortcoming such as operational condition harshness, and biological process can only be removed the BOD in the waste water from dyestuff usually, for COD, the removal effect of especially poisonous difficult degradation azoic dyestuff is not obvious, and processing cost is higher.Therefore, must carry out pre-treatment to the waste water from dyestuff that enters before aerobe is handled, reduce the colourity of waste water, improve the biodegradability of waste water from dyestuff, thereby realize the qualified discharge of waste water from dyestuff.
Hydrogen sulfide is a kind of irritating hypertoxic gas, can not only directly be detrimental to health, can cause also that in industrial production poisoning of catalyst, quality product descend, increase a series of problems such as production cost, in addition, hydrogen sulfide still causes topsoil, Greenhouse effect and one of the essential substance that damages the ozone layer, is must eliminate or one of environmental pollutant of control.Sulfur method and sulfur removal technology are numerous both at home and abroad at present, but no matter are dry method or wet desulphurization, and all exist not enough: dry desulfurization efficient is not high, sweetening agent regeneration difficulty, and Sulfur capacity is relatively low; The wet desulphurization treatment capacity is big, desulfuration efficiency height, but operate continuously, but the investment working cost is also high, and general enterprise is difficult to bear.Therefore, no matter from technology still economically the individual curing of sulfide hydrogen industrial gaseous waste, all exists big difficulty.
So the present invention has set up a kind of method of utilizing hydrogen sulfide waste gas to remove azo dye wastewater colourity, and these industrial hydrogen sulfide waste gas and waste water from dyestuff are carried out the comprehensive regulation, reaches treatment of wastes with processes of wastes against one another purpose, has important theoretical and realistic meaning.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing hydrogen sulfide waste gas to remove azo dye wastewater colourity, the synchronous removal of hydrogen sulfide in the colourity of realization waste water from dyestuff and the waste gas.
The present invention at first joins the solubility anthraquinone in the azo dye wastewater, again with hydrogen sulfide waste gas by certain technology and this azo dye wastewater contact reacts, remove the hydrogen sulfide in the waste gas when removing chroma in waste water, can also obtain the elemental sulfur of industrial use simultaneously.Realize the purpose that the treatment of wastes with processes of wastes against one another is turned waste into wealth, solved the difficult problem of waste water from dyestuff pollution and hydrogen sulfide smoke pollution.
The sulfonation anthraquinone that the present invention utilizes solubilised state in the solution earlier makes hydrogen sulfide oxidation removal in the waste gas as redox mediators, utilizes the quinhydrones of going back ortho states to make the azoic dyestuff reduction-decolor afterwards; And with the concentration control of anthraquinone in solution in 0.03-0.3 mmol/L scope.Substitute traditional anaerobe technology or the reduction of chemical reducing agent catalysis anthraquinone with the hydrogen sulfide waste gas with reductibility, not only can avoid setting up complicated biological decolouring technology or add chemical reducing agent, and accelerate the removal of hydrogen sulfide and waste water from dyestuff colourity in the waste gas greatly.
If the solubility anthraquinone concentration of adding is lower than 0.03 mmol/L, because concentration is lower, can directly cause the absorption conversion rate of hydrogen sulfide and the reduction rate of anthraquinone to descend, the removal speed of follow-up waste water from dyestuff colourity is descended.When the anthraquinone addition too high, though the removal speed of hydrogen sulfide and chroma in waste water still can be kept higher level, add the too much anthraquinone with aromatic ring structure, equal in waste water, to introduce new pollutent, will certainly increase the burden of subsequent biological treatment technology, increase follow-up processing cost.Experiment shows, at the anthraquinone of azo dye wastewater interpolation 0.03-0.3 mmol/L, is the optimizing and controlling method of removing hydrogen sulfide waste gas and chroma in waste water synchronously.
The present invention determines a kind of method of utilizing hydrogen sulfide waste gas to remove azo dye wastewater colourity.On the one hand it can be fast be cracked into colourless aromatic amine with the reducing dyes of high chroma in the waste water, and can absorb oxidation of sulfureted hydrogen on the other hand is elemental sulfur.
Principle of work of the present invention
The present invention includes hydrogen sulfide removal and dye decolored two continuous reaction process, specific as follows:
(1) removal of hydrogen sulfide.As everyone knows, at normal temperatures and pressures, hydrogen sulfide has higher solubleness in the aqueous solution, and following reaction takes place the water-soluble back of hydrogen sulfide:
H
2S+H
2O=H
++?HS
-=?2H
++S
2-
The water-soluble back of hydrogen sulfide molecule dissociates S in solution
2-And H
+, this reaction is a reversible reaction.When having the solubility anthraquinone in the solution system, 2H
+And S
2-With anthraquinone (routine anthraquinone-2-sodium, AQS) following reaction further takes place:
2H
++S
2-+AQS=S
0+H
2AQS
This reaction is a spontaneous reaction, and reaction is spontaneous carrying out to the right.This reaction just can be finished in tens of minutes at normal temperatures and pressures.Total reaction equation is as follows:
H
2S+AQS=S
0+H
2AQS
This specific character according to anthraquinone can be with its sweetening agent as a kind of hydrogen sulfide efficiently.In addition, because the sweetening agent anthraquinone is present in the middle of the liquid phase, in reactor bottom, so elemental sulfur can not influence the catalytic activity of the anthraquinone in the solution fully, there is not the poisoning of catalyst phenomenon in reaction product elemental sulfur generation back as deposition of solids.
(2) decolouring of waste water from dyestuff.After hydrogen sulfide and the anthraquinone contact reacts, the anthraquinone in the solution is converted into quinhydrones, and the azo bond that quinhydrones generates back and azoic dyestuff reacts rapidly, makes it to be reduced to colourless aromatic amine, and reaction equation is as follows:
2?H
2AQS?+R
1-N=N-R
2?=?2AQS+?R
1-N?+?N-R
2
This reaction is a spontaneous reaction equally, reacts in several minutes at normal temperatures and pressures and just can finish.Again be oxidized to anthraquinone through this reaction quinhydrones, thereby can continue to react with hydrogen sulfide.
The invention has the beneficial effects as follows
The colourity of utilizing hydrogen sulfide waste gas to remove azo dye wastewater both can make the flue gas qualified discharge, can produce the elemental sulfur of industrial use again; Simultaneously; also realized the quick removal of waste water from dyestuff colourity; its biodegradability of waste water from dyestuff after the decolouring increases substantially; be conducive to waste water from dyestuff in the further processing of follow-up sewage work; make waste water and waste gas obtain the comprehensive regulation, greatly reduce the pollution treatment cost, promoted economic benefit of enterprises; promote the conscious enforcement of enterprise to the improvement of waste water and gas, be conducive to economize on resources and protect environment.
Description of drawings
Fig. 1 is one-piece construction synoptic diagram of the present invention.Reference numeral: retort 1, water inlet pipe 2, rising pipe 3, inlet pipe 4, vapor pipe 5, circulation line 6, shore pipe 7.
Fig. 2 is that anthraquinone-2-sodium (AQS) concentration is to the influence of hydrogen sulfide removal in the waste gas.The azo dye wastewater COD that adopts is 3760 mg/L, and BOD is 25 mg/L, 800 times of colourities, pH value 8.5.The content of hydrogen sulfide is 50% in the waste gas that adopts, other be gas such as carbonic acid gas, waste gas flow velocity 1000 mL/min, repeatedly by adding the azo dye wastewater of different concns anthraquinone, with the waste water from dyestuff that do not add anthraquinone as blank.As shown in Figure 2, the anthraquinone that adds 0.03 ~ 0.3 mmol/L in the waste water can make the hydrogen sulfide in the waste gas be able to effective removal, the clearance of 30 min postcure hydrogen of ventilating all can reach more than 74%, and the hydrogen sulfide removal rate that does not add the blank of anthraquinone this moment and add 0.024 mmol/L anthraquinone only is respectively 9% and 49%.When ventilation finishes (60 min), final hydrogen sulfide removal rate all rests on about 80%, this is excessive because of adopting hydrogen sulfide waste gas in this experiment, this moment, the hydrogen Restore All that cured of the anthraquinone in the waste water was the quinhydrones attitude, but because the azoic dyestuff in the waste water is by Restore All, do not have more dyestuff and reacted with hydroquinone, quinhydrones can not be converted into anthraquinone, also just can not continue oxidation of sulfureted hydrogen.The removal speed of hydrogen sulfide increases with the increase of anthraquinone concentration in the waste water, and when anthraquinone concentration reached 0.3 mmol/L, the clearance of the 15 min hydrogen sulfide of ventilating just can reach 76%, and do not add anthraquinone blank this moment hydrogen sulfide clearance only be 6%.According to the removal effect of hydrogen sulfide, the anthraquinone in the waste water from dyestuff adds concentration should be controlled between 0.03 ~ 0.3 mmol/L, and the reaction times should be controlled at 30 min.
Fig. 3 is the influence that AQS concentration is removed chroma in waste water.As shown in Figure 3, when in waste water, adding anthraquinone, feed the decolouring that the sulfuration Hydrogen Energy significantly promotes waste water from dyestuff.When ventilation 30 min, its chroma removal rate of waste water from dyestuff that adds 0.03 ~ 0.3 mmol/L anthraquinone just can reach more than 98%, and not adding the blank of anthraquinone and the waste water from dyestuff chroma removal rate of adding 0.024 mmol/L anthraquinone this moment only is respectively 1.8% and 64%.The removal speed of waste water from dyestuff colourity is similar to the removal of hydrogen sulfide in the waste gas, also the increase with anthraquinone concentration in the waste water increases, when anthraquinone concentration reaches 0.3 mmol/L, the clearance of 15 min chroma in waste water of ventilating just can reach 98%, and do not add anthraquinone blank this moment hydrogen sulfide clearance only be 1.2%.According to the removal effect of chroma in waste water, the anthraquinone in the waste water from dyestuff adds concentration should be controlled equally between 0.03 ~ 0.3 mmol/L, and the reaction times should be controlled at 30 min.Comprehensive The above results as can be known, the removal of hydrogen sulfide is synchronous substantially in the removal of waste water from dyestuff colourity and the waste gas, therefore, with the anthraquinone concentration of 0.03 ~ 0.3 mmol/L, the reaction times of 30 min that ventilate is as the method for optimally controlling of removing hydrogen sulfide in waste water from dyestuff colourity and the gas mixture synchronously.
Embodiment
At first commercially pure anthraquinone is joined in the azo dye wastewater, after in air, fully mixing, this waste water is injected retort 1 by water inlet pipe 2, treat that the waste water liquid level rises to rising pipe 3 after, close water inlet pipe 2 and rising pipe valve 3.Open inlet pipe 4 and vapor pipe 5 valves, 1 feeds hydrogen sulfide waste gas in the retort, and reaction is carried out at normal temperatures and pressures.By the anthraquinone oxidation removal, the azoic dyestuff in the rapid reducing waste water of the quinhydrones of generation was removed chroma in waste water after hydrogen sulfide was dissolved in the waste water.Remaining unreacted hydrogen sulfide can feed in the waste water again by circulation line 6 and remove.The sulphur precipitation that the hydrogen sulfide oxidation generates can regularly be discharged from the shore pipe 7 of bottom of device.
Claims (1)
1. method of utilizing hydrogen sulfide waste gas to remove azo dye wastewater colourity, it is characterized in that: at first commercially pure anthraquinone is joined in the azo dye wastewater, after in air, fully mixing, this waste water is injected retort (1) by water inlet pipe (2), after treating that the waste water liquid level rises to rising pipe (3), close water inlet pipe (2) and rising pipe valve (3), open inlet pipe (4) and vapor pipe (5) valve, (1) feeds hydrogen sulfide waste gas in retort, reaction is carried out at normal temperatures and pressures, hydrogen sulfide is dissolved in the waste water back by the anthraquinone oxidation removal, azoic dyestuff in the rapid reducing waste water of quinhydrones that generates, chroma in waste water is removed, remain unreacted hydrogen sulfide and feed in the waste water again by circulation line (6) and remove, the sulphur precipitation that the hydrogen sulfide oxidation generates is regularly discharged from the shore pipe (7) of bottom of device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110324183 CN102417229B (en) | 2011-10-24 | 2011-10-24 | Method for removing azo dye waste water chroma by using hydrogen sulfide waste gas |
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|---|---|---|---|
| CN 201110324183 CN102417229B (en) | 2011-10-24 | 2011-10-24 | Method for removing azo dye waste water chroma by using hydrogen sulfide waste gas |
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| CN102417229A CN102417229A (en) | 2012-04-18 |
| CN102417229B true CN102417229B (en) | 2013-07-17 |
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| CN104031637B (en) * | 2014-06-24 | 2015-08-12 | 浙江大学 | A kind of azo fluorescent probe and application thereof detecting biological hydrogen sulfide |
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|---|---|---|---|---|
| JP2581726B2 (en) * | 1988-01-11 | 1997-02-12 | 三井東圧化学株式会社 | Anthraquinone dyes for sublimation transfer recording |
| CN1169335A (en) * | 1996-07-02 | 1998-01-07 | 四川川化集团公司 | Method for taking off hydrogen sulfide from mixed gas |
| CN101099919A (en) * | 2007-07-26 | 2008-01-09 | 山东大学 | Normal temperature high efficient remover for hydrogen sulfide and its preparation method and application |
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