CN109095701A - A kind of method that high-voltage pulse-Fenton handles drilling fluid waste water with high-voltage pulse-ozone co-oxidation - Google Patents
A kind of method that high-voltage pulse-Fenton handles drilling fluid waste water with high-voltage pulse-ozone co-oxidation Download PDFInfo
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- CN109095701A CN109095701A CN201811176596.5A CN201811176596A CN109095701A CN 109095701 A CN109095701 A CN 109095701A CN 201811176596 A CN201811176596 A CN 201811176596A CN 109095701 A CN109095701 A CN 109095701A
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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
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a kind of high-voltage pulse-Fenton and high-voltage pulse-ozone co-oxidation processing drilling fluid waste water method, the method in high-voltage pulse-Fenton technique, utilizes Fe in the first stage2+Catalytic action, in discharge plasma channel, be catalyzed H2O2Generate more OH, snap action hard-degraded substance in waste water, in second stage high-voltage pulse-ozone process, ozone cooperative high-voltage pulse is to the further oxidation processes of organic pollutant in waste water, by advanced optimizing technological parameter condition, realize that wastewater treatment efficiency substantially schemes to be promoted.
Description
Technical field
The invention belongs to drilling fluid field of waste water treatment, and in particular to a kind of high-voltage pulse-Fenton and high-voltage pulse-are smelly
The method of oxygen co-oxidation processing drilling fluid waste water.
Background technique
Drilling fluid waste water is a kind of complicated component, the biggish industrial wastewater of processing difficulty that oil gas field field generates, tool
There is the features such as CODcr high, coloration are high, concentration of suspension is high, salinity is high, pH value is high, complicated component, if directly arranged without processing
It puts, Soil Surrounding, water body etc. will be caused seriously to pollute.
Researchers at home and abroad have carried out a large amount of experimental study work for drilling fluid wastewater treatment, and have found
For the processing method of its characteristic, currently, the processing method of drilling fluid waste water mainly includes chemical oxidization method, microbial method, burns
Burn backfill method etc..The method achieves certain effect, but there is also degradation efficiencies that lower, pollutant removal is not thorough,
Handle the deficiencies of waste water system is single.Therefore, developing completely new technical treatment drilling fluid waste water seems further important, finds one kind
Science, environmental protection, efficient method processing drilling fluid waste water just become the project that researchers pay close attention to jointly.
High-level oxidation technology (Advanced Oxidation Process) be the 1980s environment protection field it is emerging
The concept of wastewater processing technology, high-level oxidation technology is proposed that cardinal principle is to utilize hydroxyl radical free radical by GlazeW.H et al.
The organic pollutant in waste water is acted on, can be realized quickly and thoroughly purify.The core of the technology is with hydroxyl radical free radical
As primary oxidizers, by being used in combination with for a variety of advanced oxidation processes, or suitable catalyst is added in method
The yield and efficiency of hydroxyl radical free radical are improved, the reaction time is shortened, enhances water treatment effect, compares traditional Wastewater Treatment Technology
Art, advanced oxidation processes have certain advantage.High-level oxidation technology includes high-voltage pulse technology, Ozonation, Fenton oxygen
Change method, but there are many problems in research and application aspect in single high-level oxidation technology.
For the treatment effeciency and oxidative degradation effect for improving advanced oxidation processes, domestic and international scientific research personnel has studied many efficient
Advanced oxidation processes joint technology be used for waste water processing, common includes: high-voltage pulse catalysis method, O3/H2O2Method, UV/O3
Method, Electro-Fenton process etc., but the method still has some macromolecular stabilizer knots in the drilling fluid waste water that can not thoroughly degrade
The toxic organic compound of structure.
Summary of the invention
In view of this, present invention aims at using two kinds of system combined ozone of high pressure pulse discharge, Fenton advanced oxygen
Change method handles drilling fluid waste water, and specially a kind of high-voltage pulse-Fenton and high-voltage pulse-ozone co-oxidation handle drilling fluid
The technique of waste water.The quick oxidative degradation macromolecular organic contamination of high energy active oxidation substance generated using high pressure pulse discharge
Object, and with Fenton, ozone use in conjunction to realize sewage environmental protection, efficient improvement.
For achieving the above object, technical solution as described below is specifically provided:
1, a kind of high-voltage pulse-Fenton and high-voltage pulse-ozone co-oxidation processing drilling fluid waste water method, it is described
Method includes the following steps:
1) chemical coagulation process pre-processes drilling fluid waste water: using aluminium polychloride and polyacrylamide complex coagulation
Agent pre-processes drilling fluid waste water；
2) high-voltage pulse-Fenton co-oxidation: first segment high-voltage pulse-is carried out using high pressure pulse discharge reactor
Fenton co-oxidation technique, pH value will be adjusted through step 1) treated waste water, and with sulfuric acid solution by being added into reactor,
Discharge voltage, discharge frequency, pulse width parameter are set, FeSO is first added4·7H2O adds H2O2, it is anti-to continue aeration stirring
It answers；
3) high-voltage pulse-ozone co-oxidation: second segment high-voltage pulse-ozone is carried out using high pressure pulse discharge reactor
Co-oxidation technique；It is added in discharge reactor through step 2) treated waste water, adjusts pH value with sodium hydroxide solution, if
Determine discharge voltage, discharge frequency, pulse width parameter, the air inlet of discharge reactor upper port and ozone generator are connected
It connects, carries out high-voltage pulse-ozone co-oxidation processing.
Preferably, step 1) the aluminium polychloride dosage is 5g/L；Polyacrylamide dosage is 10mg/L；PH value
It is 7, stirring rate 300r/min.
Preferably, step 2) and step 3) two-stage process high-voltage pulse reaction condition are discharge voltage 35kV, electric discharge frequency
Rate 80Hz, pulsewidth 60ns.
Preferably, step 2) H2O2Dosage 6mL/L, Fe2+Dosage 5mmol/L, pH value 3 react 90min.
Preferred: step 3) ozone dosage is 1.2g/h, and pH value 9 reacts 30min.
The beneficial effects of the invention are that: high-voltage pulse technology, the high energy of generation is used alone in drilling fluid field of waste water treatment
Active oxidation substance is sufficient not enough, not can guarantee qualified discharge after wastewater treatment；Ozone oxidation higher cost, simultaneously is used alone
And reaction condition is limited to, treatment effect is not thorough；Fenton oxidation, H in reaction process is used alone2O2Utilization rate it is lower,
It causes use cost higher, still there is a large amount of Fe after reaction in solution2+In the presence of water outlet easily causes secondary pollution to water body.And this
High-voltage pulse-the Fenton proposed and high-voltage pulse-ozone co-oxidation processing drilling fluid waste water technique are invented, in the first rank
In section high-voltage pulse-Fenton technique, Fe is utilized2+Catalytic action, in discharge plasma channel, be catalyzed H2O2It generates more
More OH, snap action hard-degraded substance in waste water, in second stage high-voltage pulse-ozone process, ozone cooperative high pressure
The further oxidation processes of organic pollutant in pulse pair waste water are polluted in sewage by advanced optimizing technological parameter condition
The processing of object has significant increase.
Detailed description of the invention
Fig. 1 is high-voltage pulse-Fenton and high-voltage pulse-ozone co-oxidation handles the device signal of drilling fluid waste water
Figure；1- high-voltage pulse power source in figure；2- working chamber；3- inlet duct；21- hollow center axis；22- cartridge type electrode；23- solution enters
Mouthful；24- taphole；25 gas outlets；
Fig. 2 is hollow center axis enlarged drawing, wherein 26 be needle electrode；
Fig. 3 is high-voltage pulse-Fenton/ high-voltage pulse-ozone co-oxidation technique to waste water decontamination indicatrix；
Specific embodiment
More detailed elaboration is carried out to the present invention below in conjunction with the accompanying drawings and the specific embodiments.
Embodiment 1
Such as Fig. 1 of reaction unit used in embodiment 1 and as shown in Figure 2: described device is by high-voltage pulse power source 1, electric discharge
Reactor, inlet duct three parts composition；The discharge reactor includes working chamber 2, the hollow center axis in working chamber
21 and cartridge type electrode 22；The working chamber includes positioned at the solution inlet 23 at top, gas outlet 25 and positioned at the molten of bottom
Liquid outlet 24, hollow center axis outer surface is welded with several with the hollow needle electrode 26 being connected to, the hollow center axis
Upper end is connected with high-voltage pulse power source and inlet duct 3, and lower end is connected with seal；The cartridge type electrode is located at working chamber
Interior and earthing pole；The inlet duct is connect with ozone generator.
The high-voltage pulse power source is DCM-200 type high-voltage pulse power source, its working principle is that: high-tension transformer will input
Single-phase alternating current boost, then will be exported in a manner of direct current after voltage commutation, and act on discharge reactor, then through needle
Formula electrode discharge makes load obtain high-voltage pulse.The hollow center axis is made of stainless steel tube, and the needle electrode is metal
Iron material matter, the cartridge type electrode are stainless steel material.
Discharge reactor discharges the air entered from needle electrode hole, and air forms countless minute bubbles in the solution,
And it is come into full contact with drilling fluid waste water.In the solution, the presence of bubble, which has, is conducive to cause bubble shelf depreciation, makees in high pressure ionization
Under, active material is rapidly and efficiently generated, by air stirring, so that active material distribution is more uniform, and promotes oxygen
Active material is generated under the action of high-pressure basic granulite, the living radical oxygen generated by electric discharge is not and oxygen
It is combined with water and generates ozone, hydrogen peroxide isoreactivity substance.
The ozone generator is SK-CFG-10C type, and specific targets are as shown in table 1:
Table 1SK-CFG-10C type ozone generator important technological parameters
| Specification | SK-CFG-10C | O3Occurrence quantity | 10g/h |
| Power supply | AC220V50Hz | Ozone concentration | 10mg/L |
| Power | 200W | Overall mass | About 15kg |
| Gas source | Air | Outer dimension | 47*37*18cm |
| Flow | 1.0m3/h | Pressure | 0.1Mpa |
Drilling fluid waste water used in the present embodiment comes from Chuan Qingtan company well site, and the drilling fluid that drilling well field uses belongs to polysulfonate
Mud system, main component have polyacrylamide amine salt, sulfonated-pheno-formoldehyde resin, SMP etc., and the waste water is in dark brown and with denseer
Foul smell.By carrying out water analysis to initial water sample, the Wastewater Pollutant index analysis result is as shown in table 2.
The content of the 2 main contamination index of drilling fluid waste water of table
Drilling fluid waste water is handled using high-voltage pulse-Fenton and high-voltage pulse-ozone co-oxidation below, by following step
It is rapid to carry out:
1) chemical coagulation process pre-processes drilling fluid waste water: using aluminium polychloride (PAC) and polyacrylamide
(PAM) compound coagulant pre-processes drilling fluid waste water；PAC dosage 5g/L, PAM dosage 10mg/L, pH value is on 7 left sides
The right side, stirring rate 300r/min；Being discharged pH is 7.64, and water body is in golden yellow, CODcr2367mg/L is down to by 14256mg/L,
CODcrRemoval rate is up to 83.39%, BOD5Removal rate is 51.28%, and turbidity removal rate 84.35% alleviates subsequent processing
Burden.
2) high-voltage pulse-Fenton co-oxidation: first segment high-voltage pulse-is carried out using high pressure pulse discharge reactor
Fenton co-oxidation technique sets discharge voltage 35kV, and discharge frequency 80Hz, pulsewidth 60ns are added in discharge reactor
A certain amount of pretreated drilling fluid waste water, adjusting pH with sulfuric acid solution is 3, and 5mmol/LFeSO is first added4·7H2O is added
6mL/LH2O2, continue aeration stirring and react 90min；
2) it high-voltage pulse-ozone co-oxidation: continues to use high pressure pulse discharge reactor and carries out second segment high-voltage pulse-
Ozone co-oxidation technique；Discharge voltage 35kV, discharge frequency 80Hz, pulsewidth 60ns are added a certain amount of in discharge reactor
1 through step) treated drilling fluid waste water, adjusting pH value with sodium hydroxide solution is 9, by the sky of discharge reactor upper port
Gas air inlet is connect with ozone generator, ozone dosage 1.2g/h, carries out high-voltage pulse-ozone co-oxidation processing
30min。
The influence that co-oxidation technique removes drilling fluid waste water COD cr, BOD5 is investigated, as a result as shown in Figure 3:
In high-voltage pulse-Fenton reaction, high-voltage pulse cooperates with Fenton to generate living radical in road as shown in Figure 3,
The organic pollutant in waste water is acted on rapidly, when process integration reacts 90min, waste water CODcrFor 304.9mg/L, BOD5For
101.2mg/L；PH is adjusted, continues to be passed through ozone reaction 30min, is discharged CODcrFor 112.6mg/L, BOD5For 38.9mg/L.
Comparative example 1
Drilling fluid waste water shown in table 2 is handled by high-voltage pulse-Fenton co-oxidation, also passes through pretreatment.This reality
It applies example and equally uses attached schematic device shown in FIG. 1, the ozone generating-device is not turned on.Discharge voltage 35kV is set, is put
A certain amount of pretreated drilling fluid waste water is added, with sulfuric acid solution tune in electric frequency 80Hz, pulsewidth 60ns in discharge reactor
Saving pH is 3, and 5mmol/LFeSO is first added4·7H2O adds 6mL/LH2O2, continue aeration stirring and react 120min.
Comparative example 2
3) the present embodiment handles drilling fluid waste water shown in table 2 by high-voltage pulse-ozone co-oxidation, also passes through pre- place
Reason.The present embodiment equally uses attached schematic device shown in FIG. 1, and ozone generating-device is opened.Discharge voltage 35kV, electric discharge frequency
A certain amount of 1 through step is added in rate 80Hz, pulsewidth 60ns in discharge reactor) treated drilling fluid waste water, use hydroxide
It is 9 that sodium solution, which adjusts pH value, the air inlet of discharge reactor upper port is connect with ozone generator, ozone dosage is
1.2g/h carries out high-voltage pulse-ozone co-oxidation and handles 120min.
Comparative example 1, comparative example 2 and embodiment 1 treated waste water are subjected to contamination index's detection, obtain as
The comparison of experimental result shown in table 3.
3 high-voltage pulse of table and Fenton oxidation processing experimental result comparison
It can be illustrated by table 3, high-voltage pulse-Fenton proposed by the present invention and high-voltage pulse-ozone co-oxidation processing are bored
The technique of well liquid waste water utilizes Fe in the first stage in high-voltage pulse-Fenton technique2+Catalytic action, in plasma discharging
In body channel, it is catalyzed H2O2More OH are generated, snap action hard-degraded substance in waste water is smelly in second stage high-voltage pulse-
In oxygen technique, ozone cooperative high-voltage pulse is to the further oxidation processes of organic pollutant in waste water, by advanced optimizing work
The treatment effect of skill Parameter Conditions, dirty water pollutant has significant increase, single compared to comparative example 1 and comparative example 2
It is of the present invention solely using high-voltage pulse-ozone and exclusive use high-voltage pulse-Fenten technique on the similarly processing time
Method is turning well liquid field of waste water treatment with very big promotion effect, can further illustrate technique of the present invention have compared with
Big application prospect meaning.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (5)
1. a kind of high-voltage pulse-Fenton and high-voltage pulse-ozone co-oxidation processing drilling fluid waste water method, feature exist
In described method includes following steps:
1) chemical coagulation process pre-processes drilling fluid waste water: using aluminium polychloride and polyacrylamide compound coagulant pair
Drilling fluid waste water is pre-processed；
2) high-voltage pulse-Fenton co-oxidation: first segment high-voltage pulse-Fenton is carried out using high pressure pulse discharge reactor
Co-oxidation technique, pH value will be adjusted through step 1) treated waste water, and with sulfuric acid solution by being added into reactor, and setting is put
Piezoelectric voltage, discharge frequency, pulse width parameter, are first added FeSO4·7H2O adds H2O2, continue aeration stirring reaction；
3) high-voltage pulse-ozone co-oxidation: second segment high-voltage pulse-ozone is carried out using high pressure pulse discharge reactor and is combined
Oxidation technology；It is added in discharge reactor through step 2) treated waste water, adjusts pH value with sodium hydroxide solution, setting is put
The air inlet of discharge reactor upper port is connect by piezoelectric voltage, discharge frequency, pulse width parameter with ozone generator,
Carry out high-voltage pulse-ozone co-oxidation processing.
2. a kind of high-voltage pulse-Fenton and high-voltage pulse-ozone co-oxidation processing drilling fluid are useless according to claim 1
The method of water, which is characterized in that step 1) the aluminium polychloride dosage is 5g/L；Polyacrylamide dosage is 10mg/
L；PH value is 7, stirring rate 300r/min.
3. a kind of high-voltage pulse-Fenton and high-voltage pulse-ozone co-oxidation processing drilling fluid are useless according to claim 1
The method of water, which is characterized in that step 2) and step 3) two-stage process high-voltage pulse reaction condition are discharge voltage 35kV, are put
Electric frequency 80Hz, pulsewidth 60ns.
4. a kind of high-voltage pulse-ozone and high-voltage pulse-Fenton co-oxidation processing drilling fluid are useless according to claim 1
The method of water, it is characterised in that: step 2) H2O2Dosage 6mL/L, Fe2+Dosage 5mmol/L, pH value 3 react 90min.
5. a kind of high-voltage pulse-ozone and high-voltage pulse-Fenton co-oxidation processing drilling fluid are useless according to claim 1
The method of water, it is characterised in that: step 3) ozone dosage is 1.2g/h, and pH value 9 reacts 30min.
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Application publication date: 20181228 |