CN103601332B - A kind of method of low-temperature plasma and light electrolysis combination treatment nitrotoluene production waste - Google Patents
A kind of method of low-temperature plasma and light electrolysis combination treatment nitrotoluene production waste Download PDFInfo
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- CN103601332B CN103601332B CN201310557219.7A CN201310557219A CN103601332B CN 103601332 B CN103601332 B CN 103601332B CN 201310557219 A CN201310557219 A CN 201310557219A CN 103601332 B CN103601332 B CN 103601332B
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Abstract
The present invention discloses a kind of method of low-temperature plasma and light electrolysis combination treatment nitrotoluene production waste, comprises the following steps: adjust ph, then enters micro cell; Water outlet removes mud after precipitation; Enter reaction of low temperature plasma device, the plasma body adopting high-pressure gas-liquid commingle discharging to produce processes; Waste water after Low Temperature Plasma Treating enters biochemical system, sewage discharge after biochemistry through adding after alkali regulates.Can less than 1500 be reduced to by the COD of nitrotoluene sewage of the present invention, and B/C can be increased to more than 0.3, in sewage, the aromatic compounds of toxic side effect can change chemical structure in addition, the biochemical of sewage is greatly improved, again after biochemical treatment, every leading indicator of water outlet all can reach first discharge standard.Stop the pollution because the discharge of nitrotoluene production waste produces, be conducive to environment protection, and realize the resource of the energy be cycled to repeat utilization.
Description
Technical field
The present invention designs a kind of chemical engineering sewage treatment process.Particularly relate to a kind of method of low-temperature plasma and light electrolysis combination treatment nitrotoluene production waste, belong to Industrial Waste Water Treatments field.
Background technology
Can produce a certain amount of sewage in the process of producing nitrotoluene, sewage mainly results from the nitrifying process in production technique, and main in sewage also have the organism such as nitrophenol sodium salt, Ortho Nitro Toluene, para-nitrotoluene, meta-nitrotoluene, toluene.The COD of this type of sewage is generally all at more than 30000mg/L, and total phenol is about 3000mg/L, and nitro compounds reaches 300mg/L, sewage complicated component, and concentration is high, and toxicity is difficult to more greatly process.
Micro electrolysis tech, being also called the technology such as Inner electrolysis, Fe3+ reduction, core-loss shape, Zero-valence Iron Process, is be widely studied and the wastewater processing technology applied.Bio-refractory waste water, the process as trade effluents such as dyestuff, printing and dyeing, agricultural chemicals, pharmacy can be preprocessing means with light electrolysis, thus realizes the decolouring of the chain rupture of macromole organic pollutant, color development and auxochrome group.
Plasma body is the 4th kind of state that material exists, and it is made up of the conducting gas ionized, comprising six kinds of typical particles, i.e. and the atom of the atom of electronics, positive ion, negative ion, excited state or molecule, ground state or molecule and photon.The method of the most frequently used artificial generation plasma body is electrion, forms a large amount of high-energy electron in electrion process, and when there being water molecules to exist, high-energy electron is in very short time (10
-7s) react form a large amount of free radical and ozone with water, in high-voltage discharge plasma, Kinds of Free Radicals a lot, mainly contains hydroxyl radical free radical OH, hydrated electron e
aq -, O, HO
2deng, they all have strong oxidisability, and the ultraviolet produced in discharge process in addition also has very strong katalysis.
Summary of the invention
The object of the present invention is to provide a kind of method of low-temperature plasma and light electrolysis combination treatment nitrotoluene production waste.
Object of the present invention can be achieved through the following technical solutions:
A method for low-temperature plasma and light electrolysis combination treatment nitrotoluene production waste, comprises following steps:
(1) by nitrotoluene production waste with sulphur acid for adjusting pH to 1 ~ 3;
(2) the nitrotoluene production waste after adjust ph enters micro cell reaction, in micro cell, the mass ratio of iron filings and gac is 1 ~ 3:1, carries out blast aeration simultaneously, and air water volume ratio is 1.5 ~ 4:1, the residence time 40 ~ 90min, water outlet enters settling tank and removes mud through precipitation;
(3) settling tank water outlet enters the reaction of reaction of low temperature plasma device, and the electric discharge of reaction of low temperature plasma device mesohigh is produced by high-frequency and high-voltage power supply, and the power of high-frequency and high-voltage power supply is 20 ~ 100w, and the power frequency of generation is 5 ~ 35kHZ; Electrion adopts pin-plate reactor, positive and negative electrode spacing 5 ~ 10mm, and discharge gas is supplied by blower fan; Reaction times 120 ~ 180min.The concrete specification of pin-plate reactor designs according to by maximum flooding quantity, and the pin electrode of pin-plate reactor generally adopts the stainless steel needle electrode of hollow, and plate electrode is generally square stainless steel plate.
(4) water outlet adjust ph to 6 ~ 8 after Low Temperature Plasma Treating, enter biochemical system, discharge after biochemical treatment.Liming or other basic solutions generally can be adopted to regulate the pH value of water outlet after Low Temperature Plasma Treating.
In step (2), air water volume ratio is preferably 2 ~ 4:1, and the residence time is preferably 50 ~ 70min.
Power frequency described in step (3) is preferably 15 ~ 25kHZ.Further be preferably 20kHZ.
Because the specific conductivity of high slat-containing wastewater is general higher, gas-liquid mixed phase electric discharge is compared and is difficult to realize, and limits the application of low-temperature plasma in high-salt wastewater field to a certain extent.The present invention's research shows Fe
2+existence can solve the electric discharge problem of high conductivity waste water to a certain extent.
In addition the major reason that low-temperature plasma physical efficiency efficiently removes water pollutant is just the ultraviolet katalysis produced in discharge process, but nitrotoluene sewage can weaken ultraviolet katalysis by colourity is too high thus reduces the processing efficiency of low-temperature plasma.
The present invention solves the problems referred to above by adopting the coupling of iron-carbon micro-electrolysis and low-temperature plasma.Iron-carbon micro-electrolysis effectively can remove colourity in nitrotoluene sewage and salinity, can produce certain ferrous ion simultaneously.Reduce specific conductivity on the one hand, produce ferrous ion and gas-liquid mixed phase electric discharge can be made to be more prone to realize, the removal of colourity can improve the efficiency of low-temperature plasma on the other hand.In the adjust ph of the nitrotoluene production waste therefore in step (1) and step (2) micro cell, iron filings and the quality of gac are than the plasma reaction effect of remarkably influenced step (3), affect wastewater treatment efficiency further.
The structure of the micro cell involved by the inventive method, reaction of low temperature plasma device and biochemical system is known in those skilled in the art.
Beneficial effect of the present invention is embodied in:
(1) sewage can complete decolouring to sewage and the part salinity removed in sewage by micro cell.
(2) the hydroxyl radical free radical OH produced in plasma reactor, hydrated electron e
aq -, O, HO
2etc. can the reacting with the organism in sewage of non-selectivity, can be effectively especially nontoxic small-molecule substance by poisonous Substance Transformations such as oil of mirbane.
(3) COD of the nitrotoluene production waste in the inventive method after reaction of low temperature plasma process can be reduced to less than 1500, and B/C can be increased to more than 0.3, in sewage, the aromatic compounds of toxic side effect can change chemical structure in addition, and the biochemical of sewage is greatly improved; Again after biochemical treatment, every leading indicator of water outlet all can reach first discharge standard.
(4) stop the pollution because the discharge of nitrotoluene production waste produces, be conducive to environment protection, and realize the resource of the energy be cycled to repeat utilization.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
Embodiment 1
(1) after producing the unified collection of the sewage produced in nitrotoluene process, equalizing tank is entered, with sulphur acid for adjusting pH to 2.
(2) sewage enters micro cell reaction, and in micro cell, the mass ratio of iron filings and gac is 2:1, carries out blast aeration simultaneously, and air water volume ratio is 2.5:1, residence time 60min, and water outlet enters settling tank and removes mud through precipitation.
(3) settling tank water outlet enters the reaction of reaction of low temperature plasma device, and the electric discharge of reaction of low temperature plasma device mesohigh is produced by high-frequency and high-voltage power supply, and the power of high-frequency and high-voltage power supply is 20 ~ 100w, and the power frequency of generation is 20kHZ; Electrion adopts pin-plate reactor, the concrete specification of pin-plate reactor designs according to by maximum flooding quantity, the pin electrode of pin-plate reactor adopts the stainless steel needle electrode of hollow, plate electrode is square stainless steel plate, positive and negative electrode spacing 8mm, discharge gas is supplied by blower fan, reaction times 120min.
(4) the water outlet adjust ph to 7.5 after Low Temperature Plasma Treating, generally can adopt liming or other basic solutions to regulate the pH value of water outlet after Low Temperature Plasma Treating.Water outlet after conciliation enters biochemical system, discharges after biochemical treatment.
Embodiment 2
(1) after producing the unified collection of the sewage produced in nitrotoluene process, equalizing tank is entered, with sulphur acid for adjusting pH to 3.
(2) sewage enters micro cell reaction, and in micro cell, the mass ratio of iron filings and gac is 3:1, carries out blast aeration simultaneously, and air water volume ratio is 2.5:1, residence time 60min, and water outlet enters settling tank and removes mud through precipitation.
(3) settling tank water outlet enters the reaction of reaction of low temperature plasma device.The electric discharge of reaction of low temperature plasma device mesohigh is produced by high-frequency and high-voltage power supply, and the power of high-frequency and high-voltage power supply is 20 ~ 100w, and the power frequency of generation is 20kHZ; Electrion adopts pin-plate reactor, and the concrete specification of pin-plate reactor designs according to by maximum flooding quantity; The pin electrode of pin-plate reactor adopts the stainless steel needle electrode of hollow, and plate electrode is square stainless steel plate, positive and negative electrode spacing 8mm, and discharge gas is supplied by blower fan, reaction times 120min.
(4) the water outlet adjust ph to 7.5 after Low Temperature Plasma Treating, generally can adopt liming or other basic solutions to regulate the pH value of water outlet after Low Temperature Plasma Treating.Water outlet after conciliation enters biochemical system, discharges after biochemical treatment.
Embodiment 3
Regulate pH to 2 in step (1); In step (2) micro cell, the mass ratio of iron filings and gac is 3:1, and other operating process are with embodiment 1.
Embodiment 4
Regulate pH to 3 in step (1); In step (2) micro cell, the mass ratio of iron filings and gac is 2:1, and other operating process are with embodiment 1.
Embodiment 5
Regulate pH to 1 in step (1); In step (2) micro cell, the mass ratio of iron filings and gac is 1:1, and other operating process are with embodiment 1.
Comparative example 1
(1) after producing the unified collection of the sewage produced in nitrotoluene process, equalizing tank is entered, with sulphur acid for adjusting pH to 0.6.
(2) sewage enters micro cell reaction, and in micro cell, the mass ratio of iron filings and gac is 4:1, carries out blast aeration simultaneously, and air water volume ratio is 2.5:1, residence time 60min, and water outlet enters settling tank and removes mud through precipitation.
(3) settling tank water outlet enters the reaction of reaction of low temperature plasma device, and the electric discharge of reaction of low temperature plasma device mesohigh is produced by high-frequency and high-voltage power supply, and the power of high-frequency and high-voltage power supply is 20 ~ 100w, and the power frequency of generation is 20kHZ; Electrion adopts pin-plate reactor, the concrete specification of pin-plate reactor designs according to by maximum flooding quantity, the pin electrode of pin-plate reactor adopts the stainless steel needle electrode of hollow, plate electrode is square stainless steel plate, positive and negative electrode spacing 8mm, discharge gas is supplied by blower fan, reaction times 120min.
(4) the water outlet adjust ph to 7.5 after Low Temperature Plasma Treating, generally can adopt liming or other basic solutions to regulate the pH value of water outlet after Low Temperature Plasma Treating.Water outlet after conciliation enters biochemical system, discharges after biochemical treatment.
Comparative example 2
(1) after producing the unified collection of the sewage produced in nitrotoluene process, equalizing tank is entered, with sulphur acid for adjusting pH to 4.
(2) sewage enters micro cell reaction, and in micro cell, the mass ratio of iron filings and gac is 1:1, carries out blast aeration simultaneously, and air water volume ratio is 2.5:1, residence time 60min, and water outlet enters settling tank and removes mud through precipitation.
(3) settling tank water outlet enters the reaction of reaction of low temperature plasma device.The electric discharge of reaction of low temperature plasma device mesohigh is produced by high-frequency and high-voltage power supply, and the power of high-frequency and high-voltage power supply is 20 ~ 100w, and the power frequency of generation is 20kHZ; Electrion adopts pin-plate reactor, and the concrete specification of pin-plate reactor designs according to by maximum flooding quantity; The pin electrode of pin-plate reactor adopts the stainless steel needle electrode of hollow, and plate electrode is square stainless steel plate, positive and negative electrode spacing 8mm, and discharge gas is supplied by blower fan, reaction times 120min.
(4) the water outlet adjust ph to 7.5 after Low Temperature Plasma Treating, generally can adopt liming or other basic solutions to regulate the pH value of water outlet after Low Temperature Plasma Treating.Water outlet after conciliation enters biochemical system, discharges after biochemical treatment.
The detected result of production waste after step (3) reaction of low temperature plasma of table 1 embodiment 1 ~ 5 and comparative example 1 ~ 2
| Step (1) pH value | Step (2) iron-carbon ratio | Testing index 1 | Testing index 2 | |
| Embodiment 1 | 2 | 2：1 | 98.1 | 97.6 |
| Embodiment 2 | 3 | 3：1 | 85.1 | 95.8 |
| Embodiment 3 | 2 | 3：1 | 97.62 | 96.24 |
| Embodiment 4 | 3 | 2：1 | 96.24 | 96.12 |
| Embodiment 5 | 1 | 1：1 | 89.1 | 95.58 |
| Comparative example 1 | 0.6 | 4：1 | 15.1 | 18.62 |
| Comparative example 2 | 4 | 1：1 | 11.03 | 21.09 |
Note: Testing index 1 is nitrotoluene compound clearance % in water outlet; Testing index 2 is COD content clearance % in water outlet.
Embodiment 6
(1) after producing the unified collection of the sewage produced in nitrotoluene process, equalizing tank is entered, with sulphur acid for adjusting pH to 1.
(2) sewage enters micro cell reaction, and in micro cell, the mass ratio of iron filings and gac is 3:1, carries out blast aeration simultaneously, and air water volume ratio is 3:1, residence time 50min, and water outlet enters settling tank and removes mud through precipitation.
(3) settling tank water outlet enters the reaction of reaction of low temperature plasma device.The electric discharge of reaction of low temperature plasma device mesohigh is produced by high-frequency and high-voltage power supply, and the power of high-frequency and high-voltage power supply is 20 ~ 100w, and the power frequency of generation is 25kHZ; Electrion adopts pin-plate reactor, and the concrete specification of pin-plate reactor designs according to by maximum flooding quantity; The pin electrode of pin-plate reactor adopts the stainless steel needle electrode of hollow, and plate electrode is square stainless steel plate, positive and negative electrode spacing 5mm, and discharge gas is supplied by blower fan, reaction times 160min.
(4) the water outlet adjust ph to 8 after Low Temperature Plasma Treating generally can adopt liming or other basic solutions to regulate the pH value of water outlet after Low Temperature Plasma Treating.Water outlet after conciliation enters biochemical system, discharges after biochemical treatment.
Embodiment 7
(1) after producing the unified collection of the sewage produced in nitrotoluene process, equalizing tank is entered, with sulphur acid for adjusting pH to 2.
(2) sewage enters micro cell reaction, and in micro cell, the mass ratio of iron filings and gac is 2:1, carries out blast aeration simultaneously, and gas-water ratio is 4:1, residence time 70min, and water outlet enters settling tank and removes mud through precipitation.
(3) settling tank water outlet enters the reaction of reaction of low temperature plasma device.The electric discharge of reaction of low temperature plasma device mesohigh is produced by high-frequency and high-voltage power supply, and the power of high-frequency and high-voltage power supply is 20 ~ 100w, and the power frequency of generation is 15kHZ; Electrion adopts pin-plate reactor, and the concrete specification of pin-plate reactor designs according to by maximum flooding quantity; The pin electrode of pin-plate reactor adopts the stainless steel needle electrode of hollow, and plate electrode is square stainless steel plate, positive and negative electrode spacing 10mm, and discharge gas is supplied by blower fan, and the reaction times is 180min.
(4) the water outlet adjust ph to 7 after Low Temperature Plasma Treating generally can adopt liming or other basic solutions to regulate the pH value of water outlet after Low Temperature Plasma Treating.Water outlet after conciliation enters biochemical system, discharges after biochemical treatment.
Table 2 embodiment 1 ~ 7 para-nitrotoluene production waste carries out the Testing index of the water quality after biochemical treatment
| Testing index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| COD | 25 | 55 | 30 | 30 | 50 | 25 | 20 |
| Nitrobenzene | 0.5 | 1.8 | 0.7 | 0.8 | 1.2 | 0.6 | 0.5 |
| SS | 12 | 28 | 15 | 15 | 25 | 14 | 12 |
| Total nitrogen | 5 | 20 | 8 | 10 | 18 | 8 | 10 |
Detected result shows, the COD of the nitrotoluene production waste in embodiment 1 ~ 7 after reaction of low temperature plasma process can be reduced to less than 1500, and B/C can be increased to more than 0.3, in sewage, the aromatic compounds of toxic side effect can change chemical structure in addition, and the biochemical of sewage is greatly improved.By the removal of the nitrotoluene production waste after Low Temperature Plasma Treating due to significantly raising and the nitrotoluene class toxic substance of B/C in embodiment 1 ~ 7, then after biochemical treatment, every leading indicator of water outlet all can reach first discharge standard.
Claims (1)
1. a method for low-temperature plasma and light electrolysis combination treatment nitrotoluene production waste, is characterized in that comprising following steps:
(1) after producing the unified collection of the sewage produced in nitrotoluene process, equalizing tank is entered, with sulphur acid for adjusting pH to 2;
(2) sewage enters micro cell reaction, and in micro cell, the mass ratio of iron filings and gac is 2:1, carries out blast aeration simultaneously, and air water volume ratio is 2.5:1, residence time 60min, and water outlet enters settling tank and removes mud through precipitation;
(3) settling tank water outlet enters the reaction of reaction of low temperature plasma device, and the electric discharge of reaction of low temperature plasma device mesohigh is produced by high-frequency and high-voltage power supply, and the power of high-frequency and high-voltage power supply is 20 ~ 100w, and the power frequency of generation is 20kHZ; Electrion adopts pin-plate reactor, the concrete specification of pin-plate reactor designs according to by maximum flooding quantity, the pin electrode of pin-plate reactor adopts the stainless steel needle electrode of hollow, plate electrode is square stainless steel plate, positive and negative electrode spacing 8mm, discharge gas is supplied by blower fan, reaction times 120min;
(4) the water outlet adjust ph to 7.5 after Low Temperature Plasma Treating, the water outlet after conciliation enters biochemical system, discharges after biochemical treatment.
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