CN1209302C - Method for treating naphthenic acid sewage by flocculation-electricity heterogeneous catalysis - Google Patents
Method for treating naphthenic acid sewage by flocculation-electricity heterogeneous catalysis Download PDFInfo
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Abstract
The present invention relates to a method for treating naphthenic acid waste water by flocculation-electricity heterogeneous catalysis. Air flotation-flocculation treatment is carried out on the naphthenic acid waste water firstly, and the pressure is 0.2 to 0.4MPa; the use quantity of medicaments is 0.01 to 0.07% of the waste water rate, and after the flocculation treatment, organic pollutants in the naphthenic acid waste water are catalyzed and oxidized on the surface of catalyst with 5 to 15V of the direct current voltage between electrodes in the electric field and 200 to 400mA per square decimeter of the electric current in an impressed electric field. Waste water can be directly discharged with reaching the standard by using the coupling technique to treat the naphthenic acid waste water, which is indicated in experimental results and the operating cost is lower.
Description
Technical field
The present invention relates to Industrial Wastewater Treatment, specifically a kind of flocculation electro multiphase catalysis is handled the naphthenic acid method for waste water.
Background technology
Naphthenic acid is the refining of petroleum byproduct, as a kind of important chemical material, is widely used in various fields such as coating, additive, sanitas.
Because naphthenic acid is strong emulsifying agent, in biochemistry pool, can cause a large amount of foamings in biochemistry pool surface, to die because of crash on the active sludge and die, the biochemical operation of serious impact makes biochemical treatment be difficult to effectively carry out.
Someone once proposed to administer naphthenic acid waste water (petrochemical complex environment protection, the second phase in 1989) with the Centrifugical extraction pretreatment process, but since when extraction the amount of carrying secretly big, react problem such as violent, make processing cost too high, be difficult to realize industrialization.
Produce in the process of process production naphthenic acid such as the naphthenic acid waste water in certain chemical plant is the byproduct after utilizing oil refining, and is acidified, contain part naphthenic acid, oil, phenol, vitriol, also have considerable chlorion, be difficult to biochemical treatment.
The air supporting method mainly is to feed or produce a large amount of bubbles in water, form water, gas and be removed material three-phase heterodisperse system, under the effect of interfacial tension, bubble floating power and hydrostaticpressure difference, bubble and the combination that is removed material are floated to the water surface, realize and water sepn.Flocculence is a dosing coagulant in water, destroys water-borne glue body particulate steady state, under certain hydraulics, by mutual collision and the gathering between micelle, is easy to isolating floss from water (Chen Fu etc., water technology and medicament complete works) thereby form.Two kinds of methods are used in combination, and pollutent is removed, and reach the purpose that purifies water.
The air supporting core is to produce microbubble.According to the mode that bubble produces, air supporting method water purification mainly adopts dispersion air air supporting method and pressure air-dissolving air-float method.
Dispersion air air supporting method is when utilizing the higher speed rotation, the waste water of peritrochanteric forms eddy current, in eddy current, be formed centrally vacuum, thereby make outside air enter rotor, air water obtains thorough mixing at the high speed rotating place, go out saliva under the effect of shearing force, gas is fine into microbubble and is spread in the water by broken.Though this method equipment is simpler, molten gas weak effect, the microbubble particle is very big, and effect is undesirable.
The pressure air-dissolving air-float method is that pressure is added to 2-5MPa, and air dissolves in the waste water, then is dispersed in the water and with the wadding piece by reliever release air formation microbubble to adhere to each other.This method advantage is molten large-minded under the high pressure, and the microbubble that discharges by reliever is fine, epigranular, and intensity is big, and come-up is stable, and is small to the disturbance of liquid, is specially adapted to the loose short grained solid-liquid separation of particulate fines.
The electric-multiphase catalytic reaction process (ZL.92106153.6) that Xie Maosong proposes, be that chemical catalysis and electrocatalysis process are combined, utilize catalyst activity component and electric activated acting in conjunction, make reaction molecular activation, can be than carrying out single reaction that can not take place under the mild reaction conditions with catalyzer.Chinese patent (ZL.92106153.6) and (ZL.00122912) respectively brew-house, fertilizer plant's wastewater processing technology are described.Utilize electricity-heterogeneous catalysis technology to build up the industrialized unit of handling fertilizer waste water, treatment capacity is 200 tons/hour, has passed through two-stage environmental administration of provinces and cities and has checked and accepted.So far operation is more than 2 years, and the waste water of treated mistake can reuse, has saved a large amount of process waters; Electricity-heterogeneous catalytic oxidation is at normal temperatures and pressures, under the synergy of electric field and catalyzer, makes larger molecular organics be converted into small molecules or CO
2And water, reduce content of harmful, thereby reach the emission standard of waste water.
Electric-multiphase catalytic oxidation and other water technology are compared, and many advantages are arranged: as the reaction conditions gentleness, carry out under the normal temperature and pressure; Water quality there is not special requirement; Working cost is low; Required equipment is simple, and floor space is little, and is easy and simple to handle; Do not produce secondary pollution; Be particularly suitable for handling the waste water of some intermediate concentration difficult degradations, big to the not high but toxicity of some concentration, as to be not suitable for biochemical treatment waste water, the also effect that can receive.
Containing in the organism trade effluent process with the electric-multiphase catalytic reaction processing, organic matter degradation is actually organism and is decomposed by catalyzed oxidation; Its reaction process is, on the one hand under the activation of extra electric field, can in the aqueous solution, cause the free radical that produces based on OH, because the non-selectivity that the OH free radical that generates has very strong oxidisability and organism is reacted makes the organism catalyzed oxidation at normal temperatures and pressures of bio-refractory become possibility; On the other hand, processed organism can selectively be carried out catalyzed oxidation at catalyst surface; Therefore, electricity-heterogeneous catalysis technology needs to realize organic degraded that under the synergy of electric field and catalyzer catalyzer and the current field condition selecting suitably to contain active ingredient just can carry out the reaction of catalyzed oxidation decomposing organic matter expeditiously.
When using air supporting-flocculation or electric-multiphase catalytic technical finesse naphthenic acid waste water separately, or effect is not ideal enough, and the waste water after the processing does not reach national specified discharge standard; Perhaps cost is too high, is unsuitable for large-scale promotion application.
Summary of the invention
The object of the present invention is to provide a kind of flocculation electro multiphase catalysis effective, that be suitable for large-scale promotion application to handle the naphthenic acid method for waste water.
For achieving the above object, technical solution of the present invention is: at first choose suitable flocculation agent and processing mode naphthenic acid waste water is carried out air supporting-flocculation treatment, pressure is 0.2～0.4MPa, and the medicament usage quantity is 0.01～0.07% of a wastewater flow rate, and the flocculation medicament that is adopted is an inorganic flocculating agent; After flocculation treatment, volts DS is 5～15V between electrode in electric field, and electric current is under the extra electric field of every square decimeter of 200～400mA, makes in the naphthenic acid waste water organic pollutant at the catalyst surface catalyzed oxidation.
Described inorganic flocculating agent (A agent) can be for a kind of in Tai-Ace S 150, polymerize aluminum chloride or the bodied ferric sulfate etc.; When the A agent is when gathering iron, at the COD of waste water
CrWhen the scope of 1200～3800mg/L, optimum quantum of utilization can be 0.025% of wastewater flow rate; Can add organic high molecular polymer coagulant aids (B agent) in the described flocculation agent, it is anionic polyacrylamide or cationic polyacrylamide, and its usage quantity is 3～7ppm; Be preferably molecular weight at the anionic polyacrylamide more than 1,400 ten thousand.
After flocculation treatment, choose the catalyzer and the current field condition of suitable active ingredient, again under the condition that extra electric field exists, make in the naphthenic acid waste water organic pollutant at the catalyst surface catalyzed oxidation, wherein said catalyzer is made up of active ingredient and carrier, is that active ingredient is supported on Al with one or more oxide compound among Fe, Ni or the Mn
2O
3Or on the absorbent charcoal carrier, wherein the weight percentage of metal component is 1～8%, is preferably 2.0～5.0%; Surplus is a carrier.
Described catalyzer can adopt immersion process for preparing, with containing the soluble chloride or the nitrate aqueous solution of metal ion, behind the impregnated carrier, leaves standstill, and roasting 4～8 hours is carried out in oven dry again under 300～450 ℃, get final product finished product;
Soluble chloride or nitrate aqueous solution concentration are 0.12～2.0mol/l in the described catalyzer, and solution is 0.8～1.5: 1 with the carrier bulk ratio; Described catalyzer leaves standstill and is meant under 25～30 ℃ of conditions and put 10～24 hours, and oven dry is to carry out in 110～130 ℃ of temperature ranges; Described catalyzer is when being carrier with the gac, and roasting is to carry out under nitrogen protection;
The present invention has following advantage:
1. the inventive method can effectively be handled the organic wastewater that produces in the naphthenic acid production process.Experimental result shows, handles naphthenic acid waste water with this flocculation technique and can reach the pre-treatment purpose, passes through the electric-multiphase catalytic effect again, can directly discharge.
2. air supporting in the inventive method-employed medicament that flocculates obtains easily, adds simply, and working cost is cheap relatively, and actual application value is arranged.
3. the electric-multiphase catalytic process operation is easy in the inventive method, and the reaction conditions gentleness is carried out at normal temperatures and pressures, is particularly suitable for handling some intermediate concentration used water difficult to degradate, and working cost is cheap, and equipment is simple, and non-secondary pollution produces.
Description of drawings
Fig. 1 is the isolated plant synoptic diagram of air supporting-flocculation.
Embodiment
Embodiment 1
Polymerize aluminum chloride is to naphthenic acid water treatment effect I
Use polymerize aluminum chloride and anionic polyacrylamide that naphthenic acid waste water is handled.COD
CrAdopt the mensuration dichromate titration (GB11914-89) of hydrochemistry oxygen requirement to analyze, as follows.
Former water COD
Cr: 1952.6mg/L, pH:6, flocculation the results are shown in Table 1.
Table 1, poly-aluminium and anionic polyacrylamide are to the naphthenic acid water treatment effect
| Polymerize aluminum chloride | Anionic polyacrylamide | Former water COD Cr (mg/L) | Water outlet COD Cr (mg/L) | Clearance (%) |
| 200ppm | 7/ppm | 1952.6 | 973.4 | 50.15 |
| 250ppm | 3.5ppm | 1952.6 | 928.7 | 52.44 |
| 250ppm | 5ppm | 1952.6 | 891.0 | 54.37 |
| 250ppm | 7ppm | 1952.6 | 772.8 | 60.42 |
*The coagulant aids molecular weight that uses is more than 1,400 ten thousand
Embodiment 2
Polymerize aluminum chloride is to naphthenic acid water treatment effect II
Use polymerize aluminum chloride and cationic polyacrylamide that naphthenic acid waste water is handled.
Former water COD
Cr: 1952.6mg/L, pH:6, experimental result sees Table 2.
Table 2, poly-aluminium and cationic polyacrylamide are to the naphthenic acid water treatment effect
| Polymerize aluminum chloride | Cationic polyacrylamide | Former water COD Cr (mg/L) | Water outlet COD Cr (mg/L) | Clearance (%) |
| 250ppm | 5ppm | 1952.6 | 1289.0 | 33.99 |
| 250ppm | 7ppm | 1952.6 | 1122.8 | 42.50 |
*The coagulant aids molecular weight that uses is about 5,000,000
Embodiment 3
Bodied ferric sulfate is to naphthenic acid water treatment effect I
With bodied ferric sulfate and anionic polyacrylamide naphthenic acid waste water is handled.
Former water COD
Cr: 1860.1mg/L, pH:6, reaction result sees Table 3.
Table 3, poly-iron and anionic polyacrylamide are to the naphthenic acid water treatment effect
| Bodied ferric sulfate | Anionic polyacrylamide | Former water COD Cr (mg/L) | Water outlet COD Cr (mg/L) | Clearance (%) |
| 200ppm | 7ppm | 1860.1 | 576.8 | 68.99 |
| 250ppm | 5ppm | 1860.1 | 682.2 | 63.11 |
| 250ppm | 7ppm | 1860.1 | 459.8 | 75.28 |
Embodiment 4
Bodied ferric sulfate is to naphthenic acid water treatment effect III
With bodied ferric sulfate and cationic polyacrylamide naphthenic acid waste water is handled.
Former water COD
Cr: 1860.1mg/L, pH:6, flocculation the results are shown in Table 4.
Table 4, poly-iron and cationic polyacrylamide are to the naphthenic acid water treatment effect
| Bodied ferric sulfate | Cationic polyacrylamide | Former water COD Cr (mg/L) | Water outlet COD Cr (mg/L) | Clearance (%) |
| 200ppm | 7ppm | 1860.1 | 534.2 | 71.82 |
| 250ppm | 5ppm | 1860.1 | 641.1 | 65.53 |
| 250ppm | 7ppm | 1860.1 | 415.9 | 77.64 |
Embodiment 5
Tai-Ace S 150 is to the naphthenic acid water treatment effect
With Tai-Ace S 150 and anionic polyacrylamide naphthenic acid waste water is handled.
Former water COD
Cr: 1850.4mg/L, pH:6, flocculation the results are shown in Table 5.
Table 5, Tai-Ace S 150 and anionic polyacrylamide are to the naphthenic acid water treatment effect
| Tai-Ace S 150 | Anionic polyacrylamide | Former water COD Cr (mg/L) | Water outlet COD Cr (mg/L) | Clearance (%) |
| 200ppm | 7ppm | 1850.4 | 1203.8 | 34.94 |
| 250ppm | 5ppm | 1850.4 | 1189.9 | 35.69 |
| 250ppm | 7ppm | 1850.4 | 1026.1 | 44.55 |
Embodiment 6
Throwing out during difference pH value
Adding under the identical medicament situation, changing the pH of former water, investigating throwing out the naphthenic acid water treatment effect.
Former water COD
Cr: 1860.1mg/L, pH:6, flocculation the results are shown in Table 6.
Table 6, under different pH values to the throwing out of naphthenic acid waste water
| PH value | 5 | 6 | 7 | 8 |
| Tai-Ace S 150 flocculation back COD Cr：(mg/L) | 1236.7 | 1001.2 | 945.3 | 934.6 |
| COD behind the poly-aluminum flocculation Cr：(mg/L) | 783.9 | 767.3 | 756.9 | 754.3 |
| Poly-iron flocculation back COD Cr：(mg/L) | 461.4 | 459.8 | 638.9 | 644.3 |
*The coagulant aids molecular weight that uses is more than 1,400 ten thousand
Heighten the pH value of water sample, the effect of poly-aluminium is almost constant; The treatment effect of poly-iron decreases; Though the Tai-Ace S 150 clearance increases, amplitude is also little, compares with the effect of poly-iron, also has than big-difference.So modulation pH is no longer considered in experiment later on, remains on the pH value about 6.
Embodiment 7
Bodied ferric sulfate is to different rings alkanoic acid water treatment effect
Experimental result shows, under similarity condition, will be much better than to use polymerize aluminum chloride and Tai-Ace S 150 with bodied ferric sulfate to the naphthenic acid water treatment effect.
Under the same conditions, with bodied ferric sulfate and cationic polyacrylamide naphthenic acid waste water is handled, effect slightly is better than with bodied ferric sulfate and anionic polyacrylamide, but therefore the cationic polyacrylamide price uses bodied ferric sulfate and anionic polyacrylamide that waste water is handled far above anionic polyacrylamide.
Be not quite similar the COD of waste water owing to produce the raw material of naphthenic acid at every turn
CrIt is bigger that value differs sometimes, also influential to treatment effect.Use bodied ferric sulfate and anionic polyacrylamide that different rings alkanoic acid waste water is handled, the bodied ferric sulfate consumption is 200ppm, and the anionic polyacrylamide consumption is 7ppm, and result sees Table 7.
Poly-iron of table 7. and anionic polyacrylamide are to different rings alkanoic acid water treatment effect
| Former water COD Cr (mg/L) | Water outlet COD Cr (mg/L) | Clearance (%) |
| 1281.6 | 566.5 | 55.80 |
| 1860.1 | 576.8 | 68.99 |
| 2416.7 | 597.4 | 75.28 |
| 3745.8 | 611.3 | 83.68 |
After using identical medicament that different rings alkanoic acid waste water is experimentized, find, along with former water COD
CrIncrease water outlet COD
CrSlightly increase, but amplitude is less, clearance but is significantly increased, even the water sample difference is described, handles rest COD in the water of back
CrCan be too not high yet.
Embodiment 8
Contrast with the eddy-current method processing efficiency
Under same experiment condition, use molten air supporting method of total head and eddy-current method that waste water is handled, adopt bodied ferric sulfate and anionic polyacrylamide that naphthenic acid waste water is handled, the bodied ferric sulfate consumption is 250ppm, the anionic polyacrylamide consumption is 7ppm, and experimental result sees Table 8.
Molten air supporting method of table 8. total head and eddy-current method contrast the wastewater treatment result
| Method | Former water COD Cr： (mg/L) | Water outlet COD Cr： (mg/L) | Clearance (%) |
| The molten air supporting method of total head | 2291.0 | 592.1 | 74.16 |
| Eddy-current method | 2291.0 | 865.8 | 62.21 |
From experimental result, under similarity condition, waste water is flocculated with the molten air supporting method of total head, treatment effect will be much better than eddy-current method.
Because naphthenic acid waste water is more difficult, COD
CrHigher, flocculation can only make former water COD
CrDrop to about 600mg/L, can't qualified discharge, add and contain 2～4% chlorion, be difficult to biochemical treatment, make flocculation back water outlet pass through the electric-multiphase catalytic reaction device again, can handle this strand waste water better.
Embodiment 9
M/Al
2O
3Preparation of catalysts:
Get the Fe (NO of 0.36mol/L
3)
3Solution 100ml is with 100 grams, 40～60 order Al
2O
3Particle is poured in the steeping fluid and is stirred, and places 10 hours, dries 2 hours down in 110 ℃, again in 400 ℃ of following roastings 3 hours, naturally cools to room temperature and makes catalyst A.The weight of metal component is in the catalyst A: Fe:2%, all the other are carrier A l
2O
3
Embodiment 10
The preparation of M/ activated-carbon catalyst:
With the Al among the mesopore activated carbon replacement embodiment 9
2O
3Powder, and under nitrogen atmosphere, carry out roasting, all the other are identical with embodiment 9, are prepared into the M/ active carbon type catalyst B that contains Fe:2%.
Embodiment 11
Electric-multiphase catalytic for the naphthenic acid waste water after the flocculation is tested I continuously
In the electric-multiphase catalytic reaction device that with PVC is material, the titanium electrode of two bands of parallel placement diamond-mesh, filling 50ml presses the catalyst A of embodiment 9 preparations, uses the pump continuous sample introduction, under certain impressed current condition, adopts different air speeds, handles.Each water sample is got numerical value after the complete equipilibrium.
20 ℃ of temperature of reaction, normal pressure, former water COD
Cr: 2267.5mg/L, pH:6 drops to 591.2mg/L after flocculation treatment.Electricity-heterogeneous catalytic reaction voltage: 14 volts, current density: the 375mA/ square decimeter, reaction back pH:7 the results are shown in table 9.
Table 9. is through the electric-multiphase catalytic result of the naphthenic acid waste water after flocculating
| Air speed (V Water∶V Catalyzer) | 1.5 | 2.0 | 2.5 | 3.0 |
| Reaction back COD Cr(mg/L) | 146.8 | 180.1 | 220.8 | 267.3 |
| Clearance (%) | 75.17 | 69.54 | 62.65 | 54.79 |
Embodiment 12
Electric-multiphase catalytic for the naphthenic acid waste water after the flocculation is tested II continuously
In reactor, the catalyst B that embodiment 10 prepares press in filling, and all the other conditions are with embodiment 11, former water COD
Cr: 2251.3mg/L, pH:6 drops to 588.1mg/L after flocculation treatment, the results are shown in table 10.
Table 10. is through the electric-multiphase catalytic result of the naphthenic acid waste water after flocculating
| Air speed (V Water∶V Catalyzer) | 1.5 | 2.0 | 2.5 | 3.0 |
| Reaction back COD Cr(mg/L) | 108.3 | 148.2 | 188.5 | 232.5 |
| Clearance (%) | 81.58 | 74.80 | 67.94 | 60.47 |
Experimental result by embodiment 11 and 12 is seen, adopts flocculation earlier, and back electric-multiphase catalytic oxidation technology is handled naphthenic acid waste water, can reach discharging standards, wherein best with the M/ active carbon type catalyst effect of absorbent charcoal carrier preparation, working cost is lower, and actual application value is arranged.
Claims (8)
1, a kind of flocculation electro multiphase catalysis is handled the naphthenic acid method for waste water, at first adopts inorganic flocculating agent that naphthenic acid waste water is carried out air supporting-flocculation treatment, and pressure is 0.2～0.4MPa, and the inorganic flocculating agent usage quantity is 0.01～0.07% of a wastewater flow rate; After the flocculation treatment, volts DS is 5～15V between electrode in electric field, and electric current is under the extra electric field of every square decimeter of 200～400mA, makes in the naphthenic acid waste water organic pollutant at the catalyst surface catalyzed oxidation.
2, flocculation electro multiphase catalysis according to claim 1 is handled the naphthenic acid method for waste water, and it is characterized in that: described inorganic flocculating agent is Tai-Ace S 150, polymerize aluminum chloride or bodied ferric sulfate.
3, flocculation electro multiphase catalysis according to claim 2 is handled the naphthenic acid method for waste water, and it is characterized in that: described inorganic flocculating agent is a bodied ferric sulfate.
4, flocculation electro multiphase catalysis according to claim 1 is handled the naphthenic acid method for waste water, and it is characterized in that: the usage quantity of described inorganic flocculating agent is 0.025% of a wastewater flow rate.
5, flocculation electro multiphase catalysis according to claim 1 is handled the naphthenic acid method for waste water, it is characterized in that: add the organic high molecular polymer coagulant aids in the described flocculation agent, it is anionic polyacrylamide or cationic polyacrylamide, and its usage quantity is 3～7ppm.
6, flocculation electro multiphase catalysis according to claim 5 is handled the naphthenic acid method for waste water, and it is characterized in that: described coagulant aids is that molecular weight is at the anionic polyacrylamide more than 1,400 ten thousand.
7, flocculation electro multiphase catalysis according to claim 1 is handled the naphthenic acid method for waste water, and it is characterized in that: described catalyzer is made up of active ingredient and carrier, is that active ingredient is supported on Al with one or more oxide compound among Fe, Ni or the Mn
2O
3Or on the absorbent charcoal carrier, wherein the weight percentage of metal component is 1～8%, and surplus is a carrier.
8, flocculation electro multiphase catalysis according to claim 7 is handled the naphthenic acid method for waste water, and it is characterized in that: the weight percentage of metal component is 2.0～5.0% in the described catalyzer.
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| CN102442748B (en) * | 2010-10-12 | 2013-11-20 | 中国石油化工股份有限公司 | Deep treatment method of naphthenic acid wastewater |
| CN106277414B (en) * | 2015-05-18 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of method that oily wastewater eliminates foam |
| CN112678986A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Treatment method of high COD heavy metal-containing sewage |
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