CN100345771C - Method for pretreating PTA wastewater through micro-electrolysis - Google Patents
Method for pretreating PTA wastewater through micro-electrolysis Download PDFInfo
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Abstract
The invention relates to a PTA wastewater pretreatment method; in particular to a method for pretreating PTA wastewater by micro-electrolysis. The steps are as follows: pretreating scrap iron, soaking in alkali liquor, removing oil, cleaning with water, and soaking in acid to remove surface oxides for later use; adding the scrap iron treated in the step A into the PTA wastewater, wherein the adding amount of the scrap iron accounts for 1-50% of the mass of the treated wastewater, adding carbon, and reacting for 0.5-2h to treat the PTA wastewater; adding alkali liquor, adjusting the pH value of the treated wastewater to 6-9, and filtering to remove precipitates. The method has the characteristics of waste treatment by waste, low treatment cost, simple operation condition and the like.
Description
Technical field:
The present invention relates to a kind of PTA pretreatment method for wastewater; Relate in particular to a kind of method of micro electrolysis pretreating PTA waste water.
Background technology:
Pure terephthalic acid (PTA) is a kind of important light textile Chemical Manufacture raw material, in its production process, produced a large amount of high concentrated organic wastewaters---PTA waste water, this waste water contains tens kinds of organism, as a large amount of acetic acid, terephthalic acid, phenylformic acid and ritalin etc., wherein except that the chain compound that contains good biodegradability, also contain biodegradability relatively poor phenyl ring shape compound, as terephthalic acid, methylbenzene etc.PTA waste water has characteristics such as temperature height, COD concentration are big, biodegradability is extremely low, and this waste water enters in the environment, will bring serious harm to water fish class and microbial growth, metabolism.
At present, domestic and international treatment PTA waste water mainly contains following method has:
1. physico-chemical process, mainly comprise absorption method, oxidation style, flocculence: the absorption method is to utilize the porousness solid matter as absorbent, make in the water one or more materials by absorption on solid surface, thereby reclaimed or removed pollutants in waste water matter.In the PTA wastewater treatment, up to standard for guaranteeing stable water outlet, remaining micro-content organism also can be removed and realizes the water resources reuse in the water, can set up advanced treatment after biological treatment, further improves purification efficiency by physical chemistry methods such as charcoal absorption, ozone or dioxide peroxide oxidations.For example adopt CHA-101 synthetic resins to carry out absorption, its absorption rate＞99%, desorption efficiency＞96% (the Wu Xikang chief editor. organic chemical waste water is administered technology).But its processing cost height, complicated operation, be easy to produce shortcomings such as secondary pollution.Oxidation style: with wet oxidation process treatment PTA waste water, oxygenant mainly is air or oxygen, at high temperature (200 ℃～370 ℃) and high pressure (2.0MPa～21.8MPa) available air oxidation down.The wet oxidation process oxidising process is carried out in liquid phase, have advantages such as applied widely, that processing efficiency is high, secondary pollution is low, rate of oxidation is fast, device is little, but its initial cost is bigger, practical value is lower, be not suitable for adopting this kind method to handle the (purifying method of waste water from dyestuff, the patent No.: SU1763378, date of application: 1992-09-23, contriver: KOPP RAISA Z (SU); KOZLOV SERGEJ YU (SU); GLEKEL FRIDA L (SU); AGZAMKHODZHAEV ANVARKHODZHA A (SU); YUSUPOV ZAJNOBIDDINYU (SU)).This method does not also have industrialized unit at home, and this method processing cost height, operational condition complexity can be used as the deep treatment method of PTA waste water.Flocculence: the terephthalic acid in the waste water can o'clock be handled in pH2～4 or 4～5.5 with ferric sulfate or iron(ic) chloride, adding polyacrylamide makes precipitation form bigger floc sedimentation, being easy to precipitation, filtering and dehydration, can improve its clearance, the rate of recovery of terephthalic acid can reach 〉=and 90%.Adopt this law can make COD value concentration reduce to 500mg/L from every liter of thousands of milligrams, terephthalic acid is reduced to 50mg/L by 2000～3000mg/L, and water outlet meets the water inlet requirement of biochemical treatment behind pH regulator.
The Wang Ying of Tian Huayu Heilungkiang water conservancy higher junior college of Xuzhou chemical engineering school once did the experimental study of flocculence treatment PTA waste water, in sour sinking pool effluent, add an amount of molysite and be aided with PAM again, utilize iron ion and TA reaction to separate out precipitation, and reach the purpose of removing COD, thereby alleviate follow-up biological degradation load, improve effluent characteristics.This kind method can reduce process water COD20% above (Tian Hua, Wang Ying .PTA Wastewater Pretreatment research [J], the special journal .2000 of Heilungkiang water, 27 (3): 51-53).This method is as characteristics such as pre-treatment processing cost height (flocculant concentration expense height), the treatment effect of PTA waste water be low.
2. biochemical treatment method:
In recent years, both at home and abroad to research being arranged with different microorganisms treatment PTA waste water more.
When doing the degraded microorganism, better to the terephthalic acid degradation property as usefulness Mycobacterium lacticolum; The mixed strains of cultivating in the also available municipal wastewater treatment plant active sludge is handled; From the active sludge of handling petrochemical wastewater with separated 261 strain aerobic bacterias the soil of para-phthalic sodium dust pollution for a long time, the part bacterial strain terephthalic acid of degrading wherein, selected bacterial strain can be degraded terephthalic acid (200mg/L) in 14 hours fully; Be separated to the strain bacterium Pseudomonas sp.T6 higher the active sludge bottom the upflow type anaerobic bacteria bed of handling Production of Terephthalic Acid waste water to the terephthalic acid degrading activity, when terephthalic acid is sole carbon source, degradation rate can reach 98%, and can degrade under aerobic condition; From the UASB of Production of Terephthalic Acid factory reactor, isolate a strain Pseudomonas sp, can be used for handling terephthalic acid, when being sole carbon source with the terephthalic acid, its degradation rate can reach≤98% (Tian Hua, Wang Ying .PTA Wastewater Pretreatment research [J], the special journal .2000 of Heilungkiang water, 27 (3): 51-53).
Bibliographical information is also arranged, earlier PTA waste water is neutralized between the pH value 7.0～7.4, redilution to COD value is about 200～1000mg/L and carries out bio-oxidation.Oxidation can proceed to final oxidation products, and terephthalic acid crystallizing and washing waste water need dilute 10 times, is about 4000～9000mg/L, BOD to the COD value
5/ COD is about 0.65, so can adopt aerobic method to carry out.(exercise questions: PROCEDE DECUISSON DE PLATRES D ' ENDUIT ET DE CONSTRUCTION DANS UN FOURROTATIF such as for example available extended aeration activated sludge process, the patent No.: ES469802, date of application: 1979-01-16, contriver: Kermer W D etai).
Under mesophilic condition, terephthalic acid can under anaerobic be degraded.When the initial concentration of PTA waste water is during less than 500mg/L, can be degraded by anerobe, the PTA of high density can not be degraded by anerobe fully, and accumulation is got up in reactor, degradation rate is slowed down, and the restraining effect certain to the anaerobic system generation (Dong Hongjun, Hailin, river. chemical fibre PTA wastewater treatment present situation and countermeasure [J], chemical industry environmental protection .2004, (24): 148-149).
Company limited of China Petrochemical Industry Luoyang Company is according to its factory's chemical fiber waste water production run and handle present situation, since 2001 January an active sludge loss difficult problem technical Analysis and tackling key problem have been carried out, adopt the residual active sludge of refinery water biochemical treatment apparatus to mix with chemical fiber waste water biochemical activity mud, utilize the difference of both sides' sludge quality to come the accelerate sludge sedimentation, thereby solve the difficult problem that the settling tank big area is run mud, guarantee the qualified discharge of chemical fibre PTA wastewater treatment water outlet.But further improving the wastewater treatment degree of depth, fundamentally improve on the active sludge performance, then also have many problems not solve, so the problem of biochemical activity sludge loss still exists.(Zhao Lihui. phthalic acid compounds aerobic biodegradation Journal of Sex Research [J], environmental chemistry .1993,12 (3): 173-178)
The traditional method of PTA wastewater treatment is that biology aerobic is handled.Biology aerobic treatment process (Yin Yuqiang, Sun Hong. definite [J] of Plant of Tianjin Petrochemical Company PTA sewage treatment process, Hebei water conservancy and hydropower technology .2003, (1): 47-48) She Ji principle is to utilize microorganism metabolism under aerobic condition vigorous, can utilize the organism in the waste water to carry out metabolism for raw material, synthetic living matter will pollute degraded simultaneously.It has following advantage: the purification efficiency height, and how treating processes does not produce foul smell; Technology maturation, so far, domestic design and the managerial experience enriched of having accumulated; Convenient management, simple to operate, strong shock resistance; And easy-to-keep biological domestication adaptation time is short, and is more extensive to environmental requirement.The weak point of biology aerobic treatment process is that energy consumption is higher, and excess sludge production is many, increased sludge treatment device investment and working cost, and retention time of sewage is long.What the PTA waste water of Shanghai Petrochem. General Plant's terylene two factories adopted is that the duplex aerating activated sludge process is handled, and this kind method treatment facility floor space is big, and construction investment and energy consumption are all than higher.
In recent years, on common biological aerobic treatment process basis, developed biological pure oxygen treatment process again.This technology make water treatment effect better, more stable, also reduced energy consumption simultaneously, reduced floor space and excess sludge production, the situation of improving environmental sanitation.At present this technology is in the application of having succeeded of Tianjin petro-chemical fiber factory.It has fully absorbed the service experience of raw waste water treatment plant success, and the core pure oxygen aeration has partly been introduced German modern technique and equipment, handles 400 * 10
4The waste water of t/a, the water outlet comprehensive qualified rate reaches 95.25%.This technical process is reasonable and practical, for the processing of PTA waste water found an avenue to success (Li Gang, Shen Lixian. Pure Terephthalic Acid Wastewater Treatment [J], Chinese biogas .1995,13 (4): 1-6).
The advantage of bio anaerobic treatment process mainly is: do not need oxygenation, energy consumption is low, and by product biogas can be used as the fuel reuse, and excess sludge production is low, and floor space is little, and is lower to nutritional requirement.But the purification efficiency to waste water is good not as aerobic treatment, and bookkeeping is strict, and capacity of resisting impact load is relatively poor.Though the purification effluent quality of anaerobic treatment method can not reach very high level, the pre-treatment before aerobic treatment is cost-effective as high concentrated organic wastewater for it.When it is generally acknowledged into water BOD＜1000mg/L, adopt aerobic method on expense, to suit, during and BOD＞1000mg/L, then adopt anaerobic process more suitable earlier.This technology has branched out novel methods such as deep-well anaerobic treatment.(Liu Xiaolin. the application [J] of anoxic biochemical processing in the petrochemical industry treatment of pure terephthalic acid wastewater, the .1996 of Environmental Pollution and Control, 18 (4): 16-19; The Zou Jiaqing chief editor. technology for treating industrial waste water [M], the .2003 of Chemical Industry Press (first version), 240-241)
The A/O biological treatment is the widest a kind of biological treatment of present range of application.It holds the length of anaerobic-aerobic, and purification efficiency is high and stable, and this kind method makes the more common biological contact oxidation process of removal ability of COD improve 5%, and possesses the ballistic ability of resisting high-concentration waste water after combining the A/O novel process of mud backflow.But its initial cost expense is more, and floor space is bigger.(the Zhao Hongbo chief editor. the experimental study [J] of microbial film A/O method treatment PTA waste water, environmental science .1994,15 (6): 47-50)
Processing for PTA and related production device discharge waste water thereof, 3rd Design Inst., Ministry of Chemical Industry's water examination two kinds of biochemical processing process of anaerobic and aerobic that once adopted have respectively been done investigative test, 1987, the pilot scale problem of certain PTA of petro-chemical corporation device wastewater treatment has been finished in Beijing's environmental protection, thereafter, Shanghai medical professionals designing institute has designed the production equipment of the aerobic treatment PTA waste water in cover pre-treatment-anaerobic digestion-the two poles of the earth, stepped major step to through engineering approaches, but for various reasons, the technology of handling at present still is difficult to make the discharging of water outlet water quality reaching standard.
1991, the PTA waste water treatment process of 3rd Design Inst., Ministry of Chemical Industry's water two-stage anoxic/aerobic (A/O) method that examination has been determined.In the anoxic section, i.e. A1 section, COD and BOD
5To a certain degree degraded is arranged, and VFA decomposes more, and the TA degraded is minimum, even zero degraded occurs; In the O1 section, competent oxygen supply makes that a large amount of aerobic floras and protozoon will be absorbed as abundant nutrition source by the organism that the A1 section is discharged and be decomposed in this section, and VFA and TA decompose in a large number, BOD
5Also reach at utmost and remove; Though the A2/O2 section repeats said process, this moment, biodegradable organism reduced in a large number, and very not active biophase is with the utilizable organic matter degradation of last small portion, and all the other meta-bolitess are then discharged system with water outlet in the lump.
Containing treatment PTA waste water on the long run test device of two-stage A/O and charcoal, the result shows: water inlet COD is 1101mg/L, the residence time is 40h, and remaining COD is respectively 82mg/L and 55mg/L in O1 section and the charcoal water outlet, and corresponding clearance is respectively 92% and 95%.This technology tool originality, easy and simple to handle, not consume alkali, shock-resistant, start time short.Afterwards, this institute adopts biomembrance process and two kinds of process treatment PTA waste water of active mud method A/O respectively, comes comparison COD degradation characteristic, and two kinds of treatment process of evidence all have COD clearance preferably, and biomembrance process COD degradation rate is higher than activated sludge process.(the Zhao Hongbo chief editor. the experimental study [J] of embrane method and mud method A/O method treatment PTA waste water, chemical industry plumbing design .1996, (3): 32-36; Yin Yuqiang, the discipline pavilion. definite [J] of Plant of Tianjin Petrochemical Company PTA sewage treatment process, Hebei water conservancy and hydropower technology .2003, (1): 47)
Raise sub-petro-chemical corporation as the maximum PTA manufacturer of China, the anaerobic composite bed technology of UASB+AF combined stuffing is adopted in the processing of PTA waste water, promptly in the pond, dose soft-filler, make the operation kept stable of anaerobic pond.Advantages such as that this kind method has is efficient, energy-conservation, operation is simple and easy.Processed waste water COD can reach 200～300mg/L, has alleviated the burden of follow-up biochemical treatment greatly; But several years needs of filler are changed once, and anaerobic sludge easily runs off, and influences treatment effect.(Qi Yizheng, Wang Shuxiong. biochemical reaction kinetics and reactor [M], Beijing: Chemical Industry Press, 1999.321-328)
Three-phase fluid bed reactor can solve the requirement of immobilized thallus to mass transfer well; Yet test shows, when immobilized thallus was filled in the general fluidized-bed reactor treatment PTA waste water, immobilization particle was because friction each other, and it is very fast wear and tear, and common fluidized-bed reactor loadings of while is more fixing, and turndown ratio is less.
Traditional common loop reactor exists several serious defectives, the ratio of internal diameter that is the diameter of diversing bucket and reactor is constant, the stationkeeping of diversing bucket in reactor, in case reactor machines with regard to the fluidisation area of immutable reactor and settling zone, gas-liquid-solid triphasic character and operational condition, turndown ratio is lower.In addition, because the aspect ratio of traditional common loop reactor is had relatively high expectations, amplify for industry and bring difficulty.When the gas-liquid-solid three-phase common loop reactor of large-scale integral type moved, energy consumption was higher, complex structure, and bubble merging is bigger, and turndown ratio is low, and maintenance cost is higher.(model person of outstanding talent, Shen Shubao etc. new bio fluidized bed processing PTA Study on wastewater [J], Treatment of Industrial Water .2004,24 (8): 40-42)
After the test of PTA factory effluent and immobilized thallus particle having been carried out certain physical, chemical property, Chen Jianmei, Sun Hong etc. have designed the new type of adjustable biological fluidized-bed reactor that a kind of energy consumption is low, the loading amount coefficient big, structure is simple, turndown ratio is big, cost is lower, be convenient to safeguard, and with the pilot plant of this reactor actual PTA factory effluent are handled.Treatment effect is good, COD clearance＞90%.(Chen Jianmei, Sun Hong etc. the Energy Saving Control [J] of purified terephthalic device wastewater treatment, chemical industry Technological Economy .1999, (17): 34-35)
Jinan chemical fibre main office introduces the equipment and the technology of Mitsui oiling PTA device, and big, the COD concentration height of wastewater flow that device is discharged is found in logical operation in a few years.The said firm analyzes its reason, by technological transformation and reinforcement operational management, thereby reduced the running cost of device, alleviated the load of Sewage treatment systems, reduced the waste of water resources and to the pollution of environment, the discharge of wastewater situation of device is improved, and COD value of waste water is reduced to about 3500mg/L from average 4600mg/L.Through great efforts, every index reaches advanced international level, the original design Spring Festival holidays economize the about 8000t of process water than the Japanese, COD content has reduced 10%～11% than the original design 3900mg/L of Japanese, year is saved the about 500t of raw material p-Xylol, year is saved the about 80t of auxiliary material Glacial acetic acid, has improved the input-output ratio of raw material greatly, has brought abundant economic benefit and environmental benefit for enterprise and society.(Liu Guohai. improve the measure [J] of PTA wastewater purifying efficiency, petrochemical complex environment protection .2000, (1): 11-14)
The PTA of polyester factory of Liaoyang petro-chemical fiber company sewage purification process adopts no excess sludge contact oxidation method, because the sewage fluctuation is bigger, often causes water outlet to exceed standard contaminate environment.At the change of water quality characteristics, this factory is constantly from the device processing power, and sewage pH optimizes operating scheme on mud operation and the treatment facility, solves a difficult technical problem.Effectively improved the PTA wastewater purifying efficiency.(Wang Tianjun. utilize gene engineering exploitation PTA wastewater treatment [J], modern chemical industry isolation technique lecture .2003, (3): 61)
Biochemical method is by degrade organism in the PTA waste water of some bacterium, because the degradation capability that has in these bacteriums is all bred by force slowly, the breeding that has is fast and its degradation capability is poor, the result causes the long processing period of PTA waste water, material consumption energy consumption height, the treatment facility investment is difficult to effective control, makes the PTA wastewater treatment become the chief component of PTA product cost, for reducing the production cost of PTA, various countries are all in the novel method of studying efficient, economic treatment PTA waste water.
For this reason, raise sub-petro-chemical corporation and Nanjing University's joint study exploitation by the gene graft technology, make up genetic engineering bacterium treatment PTA waste water new technology, pass through gene engineering, the bacterium of the high reproductive rate that screens, high degradation rate is carried out grafting, make its characteristics that both kept high reproductive rate, have the characteristic of high degradation capability again simultaneously.At present, the new technology of " constructing genetic engineering bacterium treatment PTA waste water transboundary " make good progress, and the genetic engineering bacterium with high degraded, high breeding, high flocculence successfully constructs.Lab scale studies show that, compares with present treatment PTA waste water technology, and processing efficiency improves 12 times.(Wang Tianjun. utilize gene engineering exploitation PTA wastewater treatment [J]. the lecture of modern chemical industry isolation technique, 2003, (3): 61)
The polyester technology that contains high density PTA and EG of Dong Li company exploitation, general active sludge technical costs height, shortcoming that floor space is big have been overcome, it is said that the said firm uses the new bacterial strain of latest find, can be under high temperature, high PH decomposed P TA and EG, the BOD of this system is general, and activated sludge process is high 40 times, significantly reduce the generation of mud, to take up space be 1/10 of general active sludge technology, the PTA rate of decomposition surpasses 99%.(Tian Hua, Wang Ying .PTA Wastewater Pretreatment research [J]. the special journal of Heilungkiang water, 2000.27 (3): 51)
Biochemical process is as the core processing unit of PTA waste water, has advantages such as treatment effect is stable, running cost is low, but generally without pre-treatment, has shortcomings such as capital cost height, operational condition complexity, floor space are big.
Summary of the invention:
Technical problem to be solved by this invention is in order to overcome aforesaid method processing cost height, complicated operation, to be easy to produce secondary pollution problems, simultaneously proposed a kind of method that adopts the little electrolysis process pretreating PTA waste water of iron charcoal, reached the purpose of the treatment of wastes with processes of wastes against one another for the burden that alleviates follow-up biochemical treatment.
The technical scheme of usefulness that the present invention produces is: a kind of method of pretreating PTA waste water, and its step is according to this:
A) iron filings are carried out pre-treatment, with dipping by lye, oil removing, water cleans to pH value and is 6-9, then with acid soak to remove its oxide on surface, again with clear water clean to the pH value be 6-9, standby;
B) add the iron filings of handling in the steps A in PTA waste water, the dosage of iron filings accounts for the 1%-50% of the wastewater quality of handling, and adding iron charcoal mass ratio again is 10: 1-1: 1 charcoal, and reaction 0.5-2h comes treatment PTA waste water;
C) add alkali lye, the pH value of regulating processed waste water is 6-9, removes by filter throw out.
In treatment PTA waste water process, phenomenons such as passivation appear in iron filings, when causing the treatment effect of waste water to descend, but iron filings repeating step A activate, carbon can use heating method, steaming process, solvent method, chemical oxidization method and biological process to regenerate, and is promptly reusable.
Wherein iron filings are cast iron filing, the pig iron or pure iron bits; Charcoal is gac, activated carbon fiber, coke, charcoal or wood chip.
Alkali lye is sodium hydroxide, calcium hydroxide or potassium hydroxide.Wherein steps A is a sig water, and mass percentage concentration is 1%-20%, and the mass percentage concentration of alkali lye is 30% among the step C.Acid is hydrochloric acid, sulfuric acid or nitric acid, and mass percentage concentration is 1%-20%.
Wherein the add-on of iron filings is preferably the 4%-10% of the weight of the waste water of handling among the step B; Preferred iron charcoal weight ratio is 6: 1-1: 1, and the preferred reaction time is 1-1.5h.Handle back PTA COD removal at 50%-80%.
Beneficial effect:
1. the present invention is a kind of method of utilizing the waste iron filing pretreating PTA waste water, and iron filings wherein are waste iron filing, and charcoal is a grain active carbon, and life cycle is long, has characteristics such as the treatment of wastes with processes of wastes against one another, processing cost is low, operational condition is simple.Processing cost is about 1/tens of resin adsorption method.
2. the present invention's treatment PTA waste water efficiently adopts the little electrolysis process pretreating PTA waste water of iron charcoal, makes the COD of waste water be reduced to the 50-80% of raw wastewater, alleviates the burden of follow-up biochemical treatment.
3. the present invention has characteristics such as technology is simple, treatment effect is good.
Embodiment:
Embodiment 1
Get a certain amount of waste iron iron filings earlier, with 10% soaking with sodium hydroxide 10min left and right sides oil removing, water clean to the pH value be 7, soak 30min with 18% dilute hydrochloric acid then and remove oxide on surface.During use iron filings being washed the pH value with clear water is 7.Getting 50mL and filter back PTA waste water, is that 5% (2.5g), iron carbon ratio are that 10: 1 (activated carbon is 0.25g), churning time are 1h at the iron dosage, and wastewater pH is to handle waste water under 4 the condition.The sodium hydroxide of adding 30%, the pH value of regulating processed waste water is 8, removes by filter throw out, handles back PTA COD removal and can reach 75%.
Embodiment 2
Get a certain amount of pig iron iron filings earlier, soak 10min left and right sides oil removing with 5% calcium hydroxide, water clean to pH value be 8, then with rare nitric acid dousing 30min removal oxide on surface of 12%.During use iron filings being washed the pH value with clear water is 8.Getting 50mL and filter back PTA waste water, is that 4% (2g), iron carbon ratio are that 8: 1 (activated carbon fiber is 0.3125g), churning time are 0.5h at the iron dosage, and wastewater pH is to handle waste water under 6 the condition.The calcium hydroxide of adding 30%, the pH value of regulating processed waste water is 6, removes by filter throw out, handles back PTA COD removal and can reach 70%.
Embodiment 3
Get a certain amount of pure iron iron filings earlier, soak 10min left and right sides oil removing with 15% potassium hydroxide, water clean to pH value be 9, then with 15% dilute sulphuric acid immersion 30min removal oxide on surface.During use iron filings being washed the pH value with clear water is 8.Getting 50mL and filter back PTA waste water, is that 7% (2g), iron carbon ratio are that 6: 1 (charcoal is 0.4167g), churning time are 1.5h at the iron dosage, and wastewater pH is to handle waste water under 8 the condition.The potassium hydroxide of adding 30%, the pH value of regulating processed waste water is 9, removes by filter throw out, handles back PTA COD removal and can reach 72%.
Embodiment 4
Get a certain amount of pure iron iron filings earlier, with 20% soaking with sodium hydroxide 10min left and right sides oil removing, water clean to the pH value be 8.5, soak 30min with 10% dilute hydrochloric acid then and remove oxide on surface.During use iron filings being washed the pH value with clear water is 8.5.Getting 50mL and filter back PTA waste water, is that 8% (2g), iron carbon ratio are that 4: 1 (coke is 0.625g), churning time are 2h at the iron dosage, and wastewater pH is to handle waste water under 5 the condition.The sodium hydroxide of adding 30%, the pH value of regulating processed waste water is 8.5, removes by filter throw out, handles back PTA COD removal and can reach 80%.
Embodiment 5
Get a certain amount of waste iron iron filings earlier, soak 10min left and right sides oil removing with 1% calcium hydroxide, water clean to pH value be 7, then with rare nitric acid dousing 30min removal oxide on surface of 5%.During use iron filings being washed the pH value with clear water is 7.Getting 50mL and filter back PTA waste water, is that 5% (2g), iron carbon ratio are that 1: 1 (wood chip is 2.5g), churning time are 1.5h at the iron dosage, and wastewater pH is to handle waste water under 6 the condition.The calcium hydroxide of adding 30%, the pH value of regulating processed waste water is 7, removes by filter throw out, handles back PTA COD removal and can reach 79%.
Embodiment 6
Get a certain amount of pig iron iron filings earlier, soak 10min left and right sides oil removing with 3% potassium hydroxide, water clean to pH value be 7.5, then with 20% dilute sulphuric acid immersion 30min removal oxide on surface.During use iron filings being washed the pH value with clear water is 7.5.Getting 50mL and filter back PTA waste water, is that 10% (4g), iron carbon ratio are that 2: 1 (activated carbon is 1.25g), churning time are 2h at the iron dosage, and wastewater pH is to handle waste water under 4 the condition.The potassium hydroxide of adding 30%, the pH value of regulating processed waste water is 8, removes by filter throw out, handles back PTA COD removal and can reach 67%.
Embodiment 7
Get a certain amount of waste iron iron filings earlier, with 12% soaking with sodium hydroxide 10min left and right sides oil removing, water clean to the pH value be 9, soak 30min with 6% dilute hydrochloric acid then and remove oxide on surface.During use iron filings being washed the pH value with clear water is 9.Getting 50mL and filter back PTA waste water, is that 10% (4g), iron carbon ratio are that 2: 1 (activated carbon fiber is 1.25g), churning time are 2h at the iron dosage, and wastewater pH is to handle waste water under 5 the condition.The sodium hydroxide of adding 30%, the pH value of regulating processed waste water is 9, removes by filter throw out, handles back PTA COD removal and can reach 52%.
Embodiment 8:
1) the best dosage of iron filings determines
Fixedly iron carbon ratio is 4: 1, reaction times 1h, waste water ph 4, the dosage of conversion iron filings, analyzing and processing effect.
Table 2-5 iron dosage is to the result that influences of little electrolytic trial
| Iron dosage (%) | 1 | 3 | 5 | 7 | 9 | 20 | 30 | 40 | 50 |
| Water inlet COD (mg/L) | 3796.8 | 3796.8 | 3796.8 | 3796.8 | 3796.8 | 3796.8 | 3796.8 | 3796.8 | 3796.8 |
| Water outlet COD (mg/L) | 2815.68 | 2694.72 | 2022.72 | 1948.8 | 1942.08 | 2709.02 | 2794.07 | 2888.61 | 3007.82 |
| COD clearance (%) | 25.84 | 29.03 | 46.73 | 48.67 | 48.85 | 28.65 | 26.41 | 23.92 | 20.78 |
Consider processing cost and processing efficiency, concerning PTA waste water, best iron filings dosage is about 7%.
2) best iron carbon ratio determines
Fixedly the iron dosage is 5%, reaction times 1h, waste water ph 4, conversion iron carbon ratio, analyzing and processing effect.
Table 2-6 iron carbon ratio is to the result that influences of little electrolytic trial
| Iron carbon ratio | 10∶1 | 8∶1 | 6∶1 | 4∶1 | 2∶1 | 1∶1 | 0.5∶1 |
| Water inlet COD (mg/L) | 3494.4 | 3494.4 | 3494.4 | 3494.4 | 3494.4 | 3494.4 | 3494.4 |
| Water outlet COD (mg/L) | 3158.4 | 2721.6 | 2452.8 | 2385.6 | 2352 | 2427.9 | 2492.21 |
| COD clearance (%) | 9.62 | 22.12 | 29.81 | 31.73 | 32.69 | 30.52 | 28.68 |
According to this test-results, the best iron carbon ratio of selected treatment PTA waste water is 2: 1.
3) optimum response (stirring) time determines
Fix 5% iron dosage, iron carbon ratio was got 4: 1, and waste water ph 4 changes the reaction times, the analyzing and processing effect.
After measured, get following result: as shown in Figure 3
The table 2-7 reaction times is to the result that influences of little electrolytic trial
| Reaction times (min) | 15 | 35 | 60 | 85 | 110 |
| Water inlet COD (mg/L) | 3024 | 3024 | 3024 | 3024 | 3024 |
| Water outlet COD (mg/L) | 2620.8 | 2352 | 2083.2 | 2016 | 2284.8 |
| COD clearance (%) | 13.33 | 22.22 | 31.11 | 33.33 | 24.44 |
According to above-mentioned test and analytical results, optimum reacting time is chosen to be about 80min concerning PTA waste water.
4) best pH's determines
The pH value that test records PTA waste water is about 4, shows acid, and suitable micro-electrolysis reaction for avoiding increasing processing cost, is selected under the condition of former water pH value and tests.
5) orthogonal test and checking result and discussion:
It is 3561.6mg/L that test records the preceding waste water COD of reaction
After measured, calculate, orthogonal experiments is as follows:
Table 2-8 orthogonal test table and calculation result
| Reaction times (min) | Iron dosage (%) | Iron carbon ratio | pH | COD value (mg/L) | COD clearance (%) | |
| 1 | 1(60) | 1(5) | 1(3∶1) | 1(3) | 1478.4 | 58.49 |
| 2 | 1(60) | 2(7) | 2(2∶1) | 2(4) | 1142.4 | 67.92 |
| 3 | 1(60) | 3(9) | 3(1∶1) | 3(5) | 772.8 | 78.30 |
| 4 | 2(75) | 1(5) | 2(2∶1) | 3(5) | 1512 | 57.55 |
| 5 | 2(75) | 2(7) | 3(1∶1) | 1(3) | 739.2 | 79.25 |
| 6 | 2(75) | 3(9) | 1(3∶1) | 2(4) | 1209.6 | 66.04 |
| 7 | 3(90) | 1(5) | 3(1∶1) | 2(4) | 672 | 81.13 |
| 8 | 3(90) | 2(7) | 1(3∶1) | 3(5) | 1881.6 | 47.17 |
| 9 | 3(90) | 3(9) | 2(2∶1) | 1(3) | 1008 | 71.70 |
| K 1 | 204.71 | 197.17 | 171.7 | 209.44 | ||
| K 2 | 202.84 | 194.34 | 197.17 | 215.09 | ||
| K 3 | 200 | 216.04 | 238.68 | 183.02 | ||
| k 1＝K 1/3 | 68.24 | 65.72 | 57.23 | 69.81 | ||
| k 2＝K 1/3 | 67.61 | 64.78 | 65.72 | 71.70 | ||
| k 3＝K 1/3 | 66.67 | 72.01 | 79.56 | 61.01 | ||
| Extreme difference | 1.57 | 7.23 | 22.33 | 10.69 | ||
| Excellent scheme | 1(60) | 3(9) | 3(1∶1) | 2(4) |
Can reach a conclusion from above analysis: the factor that the micro-electrolysis method pretreating PTA waste water is had the greatest impact is an iron carbon ratio, is waste water ph, iron dosage secondly, is the reaction times at last; Best testing program should be:
Iron carbon ratio is: the 3rd level, 1: 1
PH value: second level, 4
Iron dosage: the 3rd level, 9%
Reaction times: first level, 60min
Scheme under the top condition that orthogonal test is selected is not in 9 groups of tests doing, according to each factor affecting degree order, find that No. 7 test conditions is more approaching with it in the orthogonal test, different is tests the reaction times No. 7 and gets the 3rd level: 90min, and iron adds second level of measuring: 5%.
The result compares with single factor experiment, and the iron carbon ratio that orthogonal test is selected is relative with the iron dosage higher, and the reaction times is shorter.Exist the major cause of this gap to be, the result selected according to single factor experiment is on the basis of having considered processing cost and treatment effect, and the result selected with orthogonal test compares, and processing cost is relatively low.
6) proof test
The test-results of proof test
| A | A’ | B | B’ | |
| Water inlet COD (mg/L) | 3427.2 | 3427.2 | 3427.2 | 3427.2 |
| Water outlet COD (mg/L) | 873.6 | 887.04 | 719.04 | 759.36 |
| Clearance (%) | 74.50 | 74.12 | 79.02 | 77.84 |
As can be seen from the above table, the COD treatment effect under A, A ' (top condition that quadrature the is selected) test conditions is better than B, B's ' (No. 7 test conditionss in the orthogonal test), and A ' is the parallel test of A.
Test-results shows that No. 7 test conditions in the orthogonal test is the optimum process condition of micro electrolysis pretreating PTA waste water.That is:
Iron carbon ratio is: the 3rd level, 1: 1
PH value: second level, 4
Iron dosage: first level, 5%
Reaction times: the 3rd level, 90min.
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