CN104276618A - Dephenolizing extraction agent for coal chemical wastewater and use thereof and method for dephenolizing coal chemical wastewater - Google Patents
Dephenolizing extraction agent for coal chemical wastewater and use thereof and method for dephenolizing coal chemical wastewater Download PDFInfo
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- CN104276618A CN104276618A CN201410592016.6A CN201410592016A CN104276618A CN 104276618 A CN104276618 A CN 104276618A CN 201410592016 A CN201410592016 A CN 201410592016A CN 104276618 A CN104276618 A CN 104276618A
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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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
- C02F2101/00—Nature of the contaminant
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- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2305/00—Use of specific compounds during water treatment
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Abstract
The invention discloses a dephenolizing extraction agent for coal chemical wastewater and use thereof and a method for dephenolizing coal chemical wastewater by use of the extraction agent. The extraction agent can contain sec-butyl acetate or sec-butyl acetate and phenetole or sec-butyl acetate, phenetole and crown ether compounds. By dephenolizing the coal chemical wastewater, the extraction agent disclosed by the invention has an excellent dephenolizing effect, and particularly obtains an excellent removal effect of polyphenol by selecting proper components, limiting proper use level and the like. The dephenolizing extraction agent has huge application value and industrial potential productivity in the field of coal chemical wastewater treatment.
Description
Technical field
The present invention relates to extraction agent of a kind of coal chemical technology and uses thereof and the method using this extraction agent, relate more specifically to a kind of coal chemical industrial waste water dephenolize extraction agent and uses thereof and the dephenolization method of the coal chemical industrial waste water of this extraction agent of use, belong to coal chemical industrial waste water treatment agent and Application Areas thereof.
Background technology
Flourish along with China's coal chemical industry, country requires improve constantly and strengthen to industrial blowdown.Compared with other industry, coal chemical industrial waste water has the advantages that such as the water yield is large, phenol content is high, because the phenol in phenolic wastewater is a kind of protoplasma poisonous substance, directly enters in water and can make the increase of water body COD value, the hydrobiological breeding of serious harm and existence; The formation that high-concentration phenol then can suppress the photosynthesis of farm crop, reduce the vigor of enzyme, hinders cell function, destroys plant hormone, and cause phenol content in organism to increase, affect the quality of crop products.
Therefore, just because of the phenol in coal chemical industrial waste water, there is serious harm so and toxicity, only have through purification phenol removal, just can enter follow-up treatment process.
Through research, find that the aldehydes matter in coal chemical industrial waste water mainly comprises monohydric phenol and polyphenol, such as phenol, methylphenol, methyl benzenediol, xylenol, ethylphenol, methyl naphthols etc.
As the extraction process of the main method of current phenolic wastewater treatment, the method is from high-concentration phenolic wastewater, reclaim the Main Means of aldehydes matter, and it has plurality of advantages, such as: 1, not only can reclaim volatilizable phenol, and also recyclable non-volatile phenol; 2, the method equipment used is simple, dephenolize efficiency is high, be easy to realize the production automation and serialization.Just because of advantage so, extraction process industrially obtains a wide range of applications.
Apparently, in extraction process, the factors such as selection, combination, content of extraction agent is the key point implementing extraction, and these factors can affect the effect etc. of the quality of extraction product, composition, separation degree and extracting operation significantly.
Extraction agent conventional at present mainly contains light benzene, heavy benzol, heavy naptha, N-503 kerosene, vinyl acetic monomer, isopropyl ether, methyl phenyl ketone, tricresol phosphate etc.These extraction agents all have respective distinguishing feature, and such as benzene kind of extractants partition ratio is low, dephenolize efficiency is low, but cheap and easy to get; Though ether-ether kind of extractants has higher partition ratio, dephenolize efficiency is high, but water-soluble relatively large, and especially isopropyl ether boiling point is low, vapour pressure is high, volatilization loss is large, price is higher, thus limits its application; Although N-503 kerosene extraction efficiency is high, expensive, cost is caused sharply to increase.
In order to application extraction agent or other novel coal chemical industrial waste water dephenolization treating method, researcher has carried out a large amount of further investigations, and achieves some achievements, such as:
CN86108079A discloses a kind of absorption method reclaiming phenol from phenolic waste liquor, described method is applicable to from coke-oven plant, phenol is reclaimed in the waste liquid containing high phenol content that producer gas plant etc. produce, its treatment step is that phenolic waste liquor is carried out pre-treatment, iron trichloride is added after adjust pH, when charcoal absorption, synchronously add chlorine or liquid chlorine, then carry out dephenolize through distillation.
CN1056893A discloses a kind of gas sewage extracting and dephenolizing, ammonia still process treatment process, and step is: 1, gas sewage is pumped into washing tower; 2, extraction tower is pumped into except phenol; 3, enter distillation tower containing phenol extraction agent, the extraction agent of recovery can be recycled; 4, extraction after sewage directly enter ammonia still, with steam by ammonia, dissolution extraction agent stripping in water out; 5, in absorption tower, use phosphorus ammonium barren liquor Selective absorber ammonia, absorbed by raw waste water in washing tower after extraction agent cooling; 6, phosphorus ammonium pregnant liquor is resolved, is cooled to strong aqua in desorption tower.Described method has the advantage of saving cost of equipment and running expense, is applicable to the sewage disposal of coal gas or coking of coal.
CN1087607A discloses the method for a kind of waste water-tar associating dephenolize, and described method alkaline solution, as dephenolizer, comprises the steps: that (1) is water source with phenolic wastewater, adds inorganic base, be mixed with the alkaline dephenolizer of 5-30%; (2) contact with tar with above-mentioned dephenolizer, wash temperature is 15-90 DEG C, reaction times 10-60 minute, carries out phenol removal to containing phenolic tar; (3) be separated basic phenate salt aqueous phase and tar phase, decomposite phenols by sulfuric acid decomposition method or carbon dioxide decomposition method.By process like this, the phenols in waste water, oil, prussiate, nitrogen class all pollutents greatly can be reduced.
CN1365953A discloses a kind of desulfurization for petrochemical industry sour water and alkaline residue, deamination, dephenolization treating method, be included in the mixture of sour water or sour water and alkaline residue and add molysite, and by pressurized air, make the divalent sulfur in waste water generate thiosulphate and vitriol with desulfurization; Waste water after desulfurization is promoted in Gas feeding biological tower filter tank after sweetening agent retrieving arrangement, utilizes pressurized air and microorganism that ammonium salt is carried out nitrated, generates nitrate with deamination; Microorganism in biological tower filter tank such as bacterium utilizes the oxygen in pressurized air to make the phenol in waste water resolve into carbonic acid gas and water with dephenolize.The desulfuration efficiency of the method up to more than 98%, ammonia removal efficiency reaches 95%, the removal efficiency of phenol can reach 80%.
CN1450006A discloses a kind for the treatment of process of waste water, comprise adjustment, filter, extraction, dephenolize, oil removal five steps: phenolic wastewater is after crossing and filtering insolubles, make the organism in extraction agent removing waste water at the first extraction section higher alcohols and effectively reduce the content of phenol, loaded extractant removes distillation process, the higher alcohols back extraction Posterior circle steamed utilizes, organism in waste water reclaims with the form of high boiling material, extraction agent and phenolic wastewater counter-current extraction is made at the mixture of the second extraction section phosphoric acid ester and kerosene, extraction agent back extraction Posterior circle after saturated utilizes, discharged wastewater met the national standard after extraction.2.0 below mg/l can be down to by 2000-2500 mg/l through counter-current extraction sebacic acid phenolic wastewater phenol content, reach three grades of emission standards of national regulation.A large amount of phenol due to extraction and recovery, process working cost is reduced greatly, economic benefit, environmental benefit are obvious.
CN1361068A discloses a kind of method of refining oil alkaline waste water dephenolize, described method using as extraction phase unfinished gasoline with have adjusted pH value and reclaimed after the products such as naphthenic acid, crude phenols, sodium carbonate containing phenol alkaline waste water, mix through mixing tank with certain proportion, then leave standstill, after layering, isolate unfinished gasoline, thus remove the phenol in alkaline waste water.The method is simple, extraction efficiency is high, floor space is little, cost is low, and can improve the antioxidant property of oil product, does not cause secondary pollution.
CN1789164A discloses a kind of coking chemical waste water phenol and removes and recovery technology, and it first adopts ion catch electron microscopy to remove and reclaims the aldehydes matter in coking chemical waste water, then utilizes coke absorption method that the phenol in waste water is dropped to lower concentration level.This technology overcomes biological dephenolize method makes a large amount of valuable phenols can not get the defect reclaimed, and has the advantages such as flow process is short, easy to operate, precipitation agent can be recycled, and removes and reclaim to open a Tiao Xin road for Phenol.
CN1683475A discloses a kind of complex extracting and dephenolizing method for alkaline slag of smeltery, by tributyl phosphate, C
4-C
7fusel and toluene, ethylbenzene or dimethylbenzene are mixed to get extraction agent I; By C
8-C
12stable hydrocarbon, C
4-C
7fusel and toluene, ethylbenzene or dimethylbenzene are mixed to get extraction agent II; Extraction agent I is mixed complexometric extraction with alkaline residue system, and then adds extraction II, complexometric extraction, obtains three phase extraction system, and one is extracting phase mutually, and one is the phase I being rich in phenol and extraction agent I mutually, and one for being rich in sulfide and extraction agent III.The method is by utilizing tributyl phosphate, C
4-C
7fusel and improve the percentage extraction of extraction agent I when weakly alkaline containing the synergistic effect of aromatic hydrocarbon three of alkyl group side chain, by extraction agent II, extracting and separating is carried out to above-mentioned extraction phase medium sulphide content, reduce the content of phenol medium sulphide content, improve purity and the utilization ratio of phenol.
CN1834040A discloses the method for extracting and dephenolizing of a kind of high density containing phenol coal gasification waste water, described method is separated after mixing with extraction solvent methyl iso-butyl ketone (MIBK) containing phenol coal gasification waste water, obtain liquid more than solvent phase and aqueous phase, extraction solvent and crude phenols are reclaimed to solvent phase rectifying; Carry out multi-stage counter current extraction again to liquid more than aqueous phase, the extraction liquid obtained carries out the step of remaining extraction solvent recycling, and the method technique is simple, mild condition, and extraction solution can recycle.
CN101050015A discloses a kind of method for the treatment of wastewater containing phenol by high ozone concentration, and first described method is that oxygen is at ozonizer, Ozone Absorption device with ozone concentrates, be processed into the ozone that concentration is 500-1400 mg/l in holder; Then ozone enters in a counter-current configuration from the below of dephenolize reaction tower, and the phenolic wastewater being 500-3000 mg/l with concentration completes dephenolize and reacts in dephenolize reaction tower, and the contact reacts time is 10-60 second, and the concentration ratio of ozone and phenol is 1, and dephenolize rate is greater than 99%.The efficiency of the method employing high-concentrated ozone process height phenolic wastewater is high, residual ozone is decomposed into oxygen, does not bring secondary pollution, can be widely used in processing industrial phenolic wastewater, be particularly useful for processing high-concentration phenolic wastewater.
CN103496812A discloses a kind of method processing high-concentration phenol ammonia waste water, described method is in waste water extracting and dephenolizing step, n-butyl acetate is used to carry out counter-current extraction for extraction agent, re-use depickling deammoniation tower and remove sour gas in waste water and ammonia, and use solvent stripper reclaim the extraction agent in extraction phase and at the bottom of tower, obtain crude phenols product.Compared with prior art, the method effect of extracting is good, dephenolize efficiency is high, and technical process is short, processing cost is low, method is simple, easy and simple to handle, Disposal quality is reliable.
CN103496757A discloses the method for extracting and dephenolizing of a kind of high density containing phenol ammonia coal chemical industrial waste water, and at extraction tower middle and high concentration containing phenol ammonia coal chemical industrial waste water and n-butyl acetate counter current contact, tower top is extracted phase, obtains extracting phase at the bottom of tower; Extraction phase reclaims extraction agent and product crude phenols by rectifying, extraction agent recycle, and crude phenols are sold or refined, and compared with the abstraction technique related in conventional art, the recovery energy consumption of butylacetate is lower, technical process simple, the percentage extraction of phenol is high.
CN103466873A discloses a kind of ammonia removed in waste water, phenol and sour gas, and treatment effect is good, the efficient and process that cost performance is high is containing the method for high-concentration phenol, ammonia sewage; It adopts n-butyl acetate as extraction agent, and not only the rate of recovery is high, and efficient energy-saving, and cost performance is high; Phenol concentration after can making extraction in waste water is down to biochemical treatment and is entered below the phenol concentration that water requires; Adopt Double-Tower Structure to make to be separated more thorough, decrease single tower and be separated halfway drawback; Adopt counter-current extraction method to make extraction more efficient, be separated more thorough; Be worthy to be popularized and application.
CN103466874A discloses a kind of High-concentration phenol-ammonia sewage treatment method, the method is first with single tower alkali injection pressurization stripping depickling deamination, carry out extracting and dephenolizing using n-butyl acetate as extraction agent again, use solvent recovery tower and solvent stripper reclaim the extraction agent in extraction phase and at the bottom of tower, obtain crude phenols product.The method utilizes n-butyl acetate low price, with the azeotropic point of water is higher, solubleness is low, features such as energy consumption is lower in less, the removal process of loss amount in whole production process, can increases substantially the extrusion rate of phenol or reduce the process cost of extraction section.
Application number disclosed in substantive examination on March 13 in 2014 be 201410093663.2 patent of invention disclose a kind of Centrifugical extraction sewage dephenolizing process, Centrifugical extraction separation is carried out as extraction plant with supercentrifuge, dephenolize extraction agent used is one or more in diisopropyl ether, N-BUTYL ACETATE, hexone, 30% tributyl phosphate and kerosene mixture, kerosene, heavy benzol oil, and the mixed volume of described phenol-containing wastewater and extraction agent is than being 3:1 ~ 10:1.This invention adopts the method for Centrifugical extraction, but extraction agent used all exists certain problem, and such as Di Iso Propyl Ether is volatile, and loss is comparatively large, can cause water pollution once again; N-BUTYL ACETATE cost is higher, and in water, solubleness is larger; Hexone is then suitable for containing the lower waste water of phenol amount, and for containing the higher waste water of phenol, then treatment effect is bad; Then there is easily degraded of being heated in tributyl phosphate, degraded product not only easily affects its separation efficiency, and easily in extraction, forms three-phase, disturbs normal extraction process; Heavy benzol oil then easily produces secondary pollution; Kerosene mixture, kerosene are then on the high side.All there is a great defect in this kind of extractants, all need to process oil-in-water before extraction treatment, when guarantee extracts, oil-in-water content is lower than 50mg/L, otherwise carry out in treating processes, oil in water can pollute extraction agent, cause the rate of recovery of extraction agent to reduce, and then increase Solvent quantity, cost increases.
As mentioned above, disclose the multiple method of Phenol-Containing Wastewater Treatment in prior art, but still there are some shortcomings in these methods, as except phenol effect is not high, too low to polyphenol percentage extraction, it is loaded down with trivial details etc. to process.Therefore, the dephenolize extraction agent of development of new and use its dephenolization method is study hotspot and the emphasis in this field at present, also the power that is accomplished of the present invention and basic place just.
Summary of the invention
In order to development of new coal chemical industrial waste water dephenolize extraction agent and use the removing phenol in waste water method of this extraction agent, the present inventor is to this has been research deep in a large number, pay sufficient creative work and after deep scientific exploration, thus complete the present invention.
Specifically, the present invention relates generally to a kind of coal chemical industrial waste water dephenolize extraction agent, its purposes and uses the removing phenol in waste water method of this extraction agent.
More specifically, the present invention relates to following several aspect.
First aspect, the present invention relates to a kind of coal chemical industrial waste water dephenolize extraction agent.
In coal chemical industrial waste water dephenolize extraction agent of the present invention, described extraction agent comprises sec-butyl acetate, such as, can be sec-butyl acetate (being namely only made up of sec-butyl acetate, is single-component system).
In coal chemical industrial waste water dephenolize extraction agent of the present invention, as a preferred technical scheme, described extraction agent comprises sec-butyl acetate and phenyl ethyl ether, such as, can be the mixture (being namely only made up of sec-butyl acetate and phenyl ethyl ether, is bicomponent system) of sec-butyl acetate and phenyl ethyl ether.
In the mixture, the volume ratio of sec-butyl acetate and phenyl ethyl ether is 1:1.5-2.5, such as, can be 1:1.5,1:1.7,1:1.9,1:2,1:2.2,1:2.4 or 1:2.5, is preferably 1:1.8-2.2, most preferably is 1:2.
In coal chemical industrial waste water dephenolize extraction agent of the present invention, as further optimal technical scheme, described extraction agent comprises sec-butyl acetate, phenyl ethyl ether and crown ether compound, such as can be the mixture (being namely only made up of sec-butyl acetate, phenyl ethyl ether and crown ether compound, is three compositions system) of sec-butyl acetate, phenyl ethyl ether and crown ether compound.
Wherein, described crown ether compound is open chain crown ether, benzo-crown ether, cycloalkyl any one in crown ether or any multiple mixture.
Wherein, described open chain crown ether such as can be 15-hat-5 or 18-hat-6; Benzo-crown ether such as can be dibenzo-18 crown-6; Cycloalkyl crown ether such as can be dicyclohexyl-18-crown-6.
Wherein, described crown ether compound most preferably is dibenzo-18 crown-6.
In this extraction agent, the volume ratio of sec-butyl acetate and phenyl ethyl ether is 1:0.2-0.5, such as, can be 1:0.2,1:0.3,1:0.4 or 1:0.5; And
The volume mass of sec-butyl acetate and crown ether compound is than being 1:0.002-0.008 ml/g, namely every 1 ml sec-butyl acetate uses 0.002-0.008 g crown compound, such as, can be 1:0.002 ml/g, 1:0.004 ml/g, 1:0.006 ml/g or 1:0.008 ml/g.
Most preferably, the volume mass being 1:0.2-0.5 and sec-butyl acetate and crown ether compound in the volume ratio meeting above-mentioned sec-butyl acetate and phenyl ethyl ether compares for while 1:0.002-0.008 ml/g, also need satisfied following condition: in this extraction agent, phenyl ethyl ether is 1:0.006-0.012 ml/g with the volume mass ratio of crown ether compound, namely every 1 ml phenyl ethyl ether uses 0.006-0.012 g crown ether compound, such as can be 1:0.006 ml/g, 1:0.007 ml/g, 1:0.008 ml/g, 1:0.009 ml/g, 1:0.01 ml/g, 1:0.011 ml/g or 1:0.012 ml/g.
Through large quantifier elimination, the present inventor finds:
(1) when described extraction agent is sec-butyl acetate, its decreasing ratio for phenolic compound especially polyphenol compound will be significantly higher than the decreasing ratio of n-butyl acetate of the prior art.
(2) unexpectedly, when adding phenyl ethyl ether further wherein, the decreasing ratio of polyphenol compound can be improved further.
(3) more unexpectedly, when on the basis adding phenyl ethyl ether, continue further to add crown ether compound, and when making the consumption of three within the scope of special value, the decreasing ratio of polyphenol compound reaches optimum, and having minimum Solvent quantity (creating utilization ratio and most effective, the plurality of advantages such as cost is minimum), this proves sec-butyl acetate, has played non-obvious mutual trade-off effect between phenyl ethyl ether and crown ether compound three.
Second aspect, the present invention relates to the purposes of above-mentioned coal chemical industrial waste water dephenolize extraction agent in coal chemical industrial waste water phenol removal.
The present inventor finds, above-mentioned extraction agent can remove the pollutent phenolic compound in coal chemical industrial waste water, especially polyphenol compound, thus can be applied in the phenol removal of coal chemical industrial waste water, has good industrial applications prospect and potentiality.
3rd aspect, the present invention relates to a kind of dephenolization method using the coal chemical industrial waste water of above-mentioned coal chemical industrial waste water dephenolize extraction agent.
In described dephenolization method of the present invention, when described extraction agent is the mixture of sec-butyl acetate, phenyl ethyl ether and crown ether compound, first crown ether compound is joined in sec-butyl acetate, abundant stirring, dissolving mix, then phenyl ethyl ether is added, again stir, obtain described extraction agent.
In described dephenolization method of the present invention, when the volume ratio of described extraction agent and pending coal chemical industrial waste water is 1:10-70, such as, can be 1:10,1:20,1:30,1:40,1:50,1:60 or 1:70.
In described dephenolization method of the present invention, its equipment therefor, step etc. are all same as the corresponding operating in the earlier application CN103466874A of the applicant, and this is no longer going to repeat them.
As mentioned above, the invention provides a kind of coal chemical industrial waste water dephenolize extraction agent, its purposes and use the coal chemical industrial waste water dephenolization method of this extraction agent, by the selection of extraction agent component and respective content, thus achieve excellent dephenolization effect, especially very high removal effect is had for polyphenol compound, be much better than removal methods of the prior art, have huge application prospect and potentiality in coal chemical technology.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
coal Chemical Industry phenolic wastewater
The phenolic wastewater of certain Coal Chemical Industry is sampled, then measures total phenol content wherein, monohydric phenol content and polyphenol content (measuring method is known, and this is no longer going to repeat them), shown in each content table specific as follows:
| Project | Total phenol content | Monohydric phenol content | Polyphenol content |
| Content (mg/L) | 18950 | 10153 | 8797 |
Unless otherwise defined, all use this Coal Chemical Industry phenolic wastewater as phenol removal sample in all embodiments below.
embodiment 1: the removal effect of different extraction agent is investigated
Processed according to the method for CN103466874A embodiment one, parameter and step by above-mentioned phenol removal sample, difference part is that the volume ratio using following extraction agent and described extraction agent and waste water is 1:30:
Extraction agent 1: n-butyl acetate.
Extraction agent 2: sec-butyl acetate.
Extraction agent 3: the mixture of sec-butyl acetate and phenyl ethyl ether, both volume ratios are 1:2.
Extraction agent 4: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, the volume ratio of sec-butyl acetate and phenyl ethyl ether is that the volume mass of 1:0.2, sec-butyl acetate and dibenzo-18 crown-6 is than being 1:0.002 ml/g, namely phenyl ethyl ether and the volume mass of dibenzo-18 crown-6 are than being 1:0.01 ml/g, and the content meeting these three kinds of components limits.
Wherein, the dibenzo-18 crown-6 meeting the restriction of above-mentioned consumption joins in sec-butyl acetate by the preparation method of extraction agent 4, after abundant stirring, dissolving mix, add phenyl ethyl ether again, again stir, thus obtain described extraction agent 4 (all extraction agents be made up of these three kinds of components that relates to all use the method to be prepared, and repeat no longer one by one) below.
Through measuring, the various phenol content in processed waste water and decreasing ratio are listed in table 1.
Table 1. processes rear various phenol content (mg/L) and decreasing ratio (%)
From table 1, relative to n-butyl acetate of the prior art, in the present invention when extraction agent is sec-butyl acetate, total phenol removal rate has had and has significantly improved, although monohydric phenol decreasing ratio is about the same, unexpectedly, polyphenol decreasing ratio has had and significantly improves.And when extraction agent is the mixture of sec-butyl acetate and phenyl ethyl ether, find that total phenol removal rate and polyphenol decreasing ratio have all had further raising, especially the raising of polyphenol decreasing ratio is more obvious.Be more unexpectedly, when extraction agent is the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, total phenol removal rate, monohydric phenol decreasing ratio and polyphenol decreasing ratio have all had and have significantly improved, especially polyphenol almost removes completely, this is surprising, also demonstrates these three kinds of components and has played beyond thought synergy and effect.
embodiment 2: the removal effect of different crown ether is investigated
The present embodiment is implemented according to the same procedure of above-described embodiment 1, difference part is only the 15-hat-5 of consumptions such as being replaced with respectively by " dibenzo-18 crown-6 " in extraction agent 4,18-is preced with-6 and dicyclohexyl-18-crown-6, extraction agent after so replacing is distinguished called after extraction agent 5, extraction agent 6 and extraction agent 7, namely has following corresponding relation:
Extraction agent 5: the mixture of sec-butyl acetate, phenyl ethyl ether and 15-hat-5.
Extraction agent 6: the mixture of sec-butyl acetate, phenyl ethyl ether and 18-hat-6.
Extraction agent 7: the mixture of sec-butyl acetate, phenyl ethyl ether and dicyclohexyl-18-crown-6.
Through measuring, the various phenol content in processed waste water and decreasing ratio are listed in table 2, but in order to more clear carry out contrasting just, and the extraction results of extraction agent 4 to be listed in the lump.
Table 2. processes rear various phenol content (mg/L) and decreasing ratio (%)
From table 2, when extraction agent is sec-butyl acetate, during the mixture of phenyl ethyl ether and crown ether compound, the decreasing ratio of concrete selection on phenol of crown ether compound has remarkably influenced, wherein dicyclohexyl-18-crown-6 has best removal effect to total phenol removal rate especially polyphenol decreasing ratio, and other crown ether compound is as open chain crown ether (such as 15-hat-5 or 18-hat-6), cycloalkyl crown ether (such as dicyclohexyl-18-crown-6) are although have good removal effect while not comprising crown ether (be higher than) to monohydric phenol wherein, but the decreasing ratio of polyphenol is wanted significantly on the contrary lower than dibenzo-18 crown-6, even outline is lower than the effect (contrasting with extraction agent 3) when not comprising crown ether.The crown ether which illustrating also not all can play the effect simultaneously significantly improving total phenol and polyphenol decreasing ratio, and only have dibenzo-18 crown-6 can produce beyond thought synergy with other two kinds of components, therefore in the present invention, most preferably crown ether is dibenzo-18 crown-6.
embodiment 3: the investigation of sec-butyl acetate and phenyl ethyl ether amount ratio in extraction agent 3
Use extraction agent 3, the present embodiment is implemented according to the same procedure of above-described embodiment 1, difference part is only the volume ratio changing sec-butyl acetate and phenyl ethyl ether in extraction agent 3, and the various phenol content in concrete volume ratio and processed waste water, decreasing ratio are listed in table 3.
Table 3. processes rear various phenol content (mg/L) and decreasing ratio (%)
From table 3, when extraction agent is the mixture of sec-butyl acetate and phenyl ethyl ether, both volume ratios have significant impact for removal effect, volume ratio is preferably 1:1.8-2.2, when exceeding this scope, decreasing ratio all will be caused to have remarkable reduction, and finding most preferably to be 1:2 simultaneously.
embodiment 4: the investigation of sec-butyl acetate and phenyl ethyl ether amount ratio in extraction agent 4
Use extraction agent 4, implement the present embodiment according to the same procedure of above-described embodiment 1, difference part is only the volume ratio changing sec-butyl acetate and phenyl ethyl ether in extraction agent 4, specific as follows:
Extraction agent 8: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, wherein sec-butyl acetate and phenyl ethyl ether volume ratio are the volume mass ratio of 1:2, sec-butyl acetate and dibenzo-18 crown-6 is 1:0.008 ml/g, and namely the volume mass of phenyl ethyl ether and dibenzo-18 crown-6 is than being 1:0.004 ml/g.
Extraction agent 9: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, wherein sec-butyl acetate and phenyl ethyl ether volume ratio are the volume mass ratio of 1:1.5, sec-butyl acetate and dibenzo-18 crown-6 is 1:0.0075 ml/g, and namely the volume mass of phenyl ethyl ether and dibenzo-18 crown-6 is than being 1:0.005 ml/g.
Extraction agent 10: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, wherein sec-butyl acetate and phenyl ethyl ether volume ratio are the volume mass ratio of 1:2.5, sec-butyl acetate and dibenzo-18 crown-6 is 1:0.005 ml/g, and namely the volume mass of phenyl ethyl ether and dibenzo-18 crown-6 is than being 1:0.002 ml/g.
Through measuring, the various phenol content in processed waste water and decreasing ratio are listed in table 4, but in order to more clear carry out contrasting just, and the extraction results of extraction agent 4 to be listed in the lump.
Table 4. processes rear various phenol content (mg/L) and decreasing ratio (%)
From table 4, when the sec-butyl acetate when using extraction agent to be only made up of sec-butyl acetate and phenyl ethyl ether and the preferred volume ratio of phenyl ethyl ether, this preferred volume ratio is not not only preferable range when extraction agent is made up of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, significantly reduce the decreasing ratio of various phenol on the contrary, even will be inferior to removal effect when being only made up of sec-butyl acetate and phenyl ethyl ether.This proves in three compositions system, the preferred volume ratio of sec-butyl acetate and phenyl ethyl ether there occurs unexpected change completely, and preferred volume ratio during two-pack has not been suitable for three components (the phase application quantity that should meet during three components in " summary of the invention " limits) completely.
embodiment 5: the investigation of sec-butyl acetate and dibenzo-18 crown-6 amount ratio in extraction agent 4
Use extraction agent 4, implement the present embodiment according to the same procedure of above-described embodiment 1, difference part is only the volume mass ratio changing sec-butyl acetate and dibenzo-18 crown-6 in extraction agent 4, specific as follows:
Extraction agent 11: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, wherein sec-butyl acetate and phenyl ethyl ether volume ratio are the volume mass ratio of 1:0.2, sec-butyl acetate and dibenzo-18 crown-6 is 1:0.001 ml/g, and namely the volume mass of phenyl ethyl ether and dibenzo-18 crown-6 is than being 1:0.005 ml/g.
Extraction agent 12: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, wherein sec-butyl acetate and phenyl ethyl ether volume ratio are the volume mass ratio of 1:0.3, sec-butyl acetate and dibenzo-18 crown-6 is 1:0.0045 ml/g, and namely the volume mass of phenyl ethyl ether and dibenzo-18 crown-6 is than being 1:0.015 ml/g.
Extraction agent 13: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, wherein sec-butyl acetate and phenyl ethyl ether volume ratio are the volume mass ratio of 1:0.4, sec-butyl acetate and dibenzo-18 crown-6 is 1:0.008 ml/g, and namely the volume mass of phenyl ethyl ether and dibenzo-18 crown-6 is than being 1:0.02 ml/g.
Extraction agent 14: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, wherein sec-butyl acetate and phenyl ethyl ether volume ratio are the volume mass ratio of 1:0.5, sec-butyl acetate and dibenzo-18 crown-6 is 1:0.007 ml/g, and namely the volume mass of phenyl ethyl ether and dibenzo-18 crown-6 is than being 1:0.014 ml/g.
Through measuring, the various phenol content in processed waste water and decreasing ratio are listed in table 5, but in order to more clear carry out contrasting just, and the extraction results of extraction agent 4 to be listed in the lump.
Table 5. processes rear various phenol content (mg/L) and decreasing ratio (%)
From table 5, when phenyl ethyl ether being compared in the limited range not in " summary of the invention " when the volume mass ratio changing sec-butyl acetate and dibenzo-18 crown-6 in extraction agent 4 with the volume mass of dibenzo-18 crown-6, even if time in the limited range of the volume ratio of sec-butyl acetate and phenyl ethyl ether in " summary of the invention ", but removal effect still has and significantly reduces, even will far inferior to the removal effect (comparing with the effect of extraction agent 5-7) using other crown ether.
embodiment 6: the investigation of three components amount ratio in extraction agent 4
Use extraction agent 4, implement the present embodiment according to the same procedure of above-described embodiment 1, difference part is only to change sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6 amount ratio in extraction agent 4, specific as follows:
Extraction agent 15: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, the volume ratio of sec-butyl acetate and phenyl ethyl ether is that the volume mass of 1:0.3, sec-butyl acetate and dibenzo-18 crown-6 is than being 1:0.0024 ml/g, namely phenyl ethyl ether and the volume mass of dibenzo-18 crown-6 are than being 1:0.008 ml/g, and the content meeting these three kinds of components limits.
Extraction agent 16: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, the volume ratio of sec-butyl acetate and phenyl ethyl ether is that the volume mass of 1:0.4, sec-butyl acetate and dibenzo-18 crown-6 is than being 1:0.0048 ml/g, namely phenyl ethyl ether and the volume mass of dibenzo-18 crown-6 are than being 1:0.012 ml/g, and the content meeting these three kinds of components limits.
Extraction agent 17: the mixture of sec-butyl acetate, phenyl ethyl ether and dibenzo-18 crown-6, the volume ratio of sec-butyl acetate and phenyl ethyl ether is that the volume mass of 1:0.5, sec-butyl acetate and dibenzo-18 crown-6 is than being 1:0.003 ml/g, namely phenyl ethyl ether and the volume mass of dibenzo-18 crown-6 are than being 1:0.006 ml/g, and the content meeting these three kinds of components limits.
Through measuring, the various phenol content in processed waste water and decreasing ratio are listed in table 6, but in order to more clear carry out contrasting just, and the extraction results of extraction agent 4 to be listed in the lump.
Table 6. processes rear various phenol content (mg/L) and decreasing ratio (%)
In addition, consolidated statement 4-table 6 is visible, in three compositions system, only have that " volume ratio of sec-butyl acetate and phenyl ethyl ether is 1:0.2-0.5, the volume mass of sec-butyl acetate and crown ether compound is than being 1:0.002-0.008 ml/g, but following condition should be met: in the mixture, phenyl ethyl ether is 1:0.006-0.012 ml/g with the volume mass ratio of crown ether compound " time, just can obtain best synergy, this is completely beat all, its reason may be the selection due to suitable amounts, and make three compositions system to the extraction coefficient of various phenol, extracting powers etc. have had best performance, contriver further will further investigate this.
As mentioned above, the invention provides a kind of coal chemical industrial waste water dephenolize extraction agent, purposes and use this extraction agent to carry out the method for phenol removal to coal chemical industrial waste water, contriver finds, use sec-butyl acetate can have better dephenolization effect than n-butyl acetate of the prior art, and when adding the phenyl ethyl ether of specific consumption further, dephenolization effect has had further improvement.Unexpectedly, when adding crown ether compound especially dibenzo-18 crown-6 further in above-mentioned bicomponent system, and the consumption of three kinds of components in certain specified range time, achieve the most excellent de-effect.When changing the amount ratio in this specified range, removal effect all will be caused to have obvious reduction, even lower than effect during two-pack, will this demonstrate that obtaining of this best effect is three kinds of components, specific consumption limits and the comprehensive collaborative result played a role.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. a coal chemical industrial waste water dephenolize extraction agent, is characterized in that: described extraction agent comprises sec-butyl acetate.
2. extraction agent as claimed in claim 1, is characterized in that: described extraction agent comprises sec-butyl acetate and phenyl ethyl ether.
3. extraction agent as claimed in claim 2, is characterized in that: the volume ratio of described sec-butyl acetate and phenyl ethyl ether is 1:1.5-2.5.
4. extraction agent as claimed in claim 2 or claim 3, is characterized in that: described extraction agent comprises sec-butyl acetate, phenyl ethyl ether and crown ether compound.
5. extraction agent as claimed in claim 4, is characterized in that: described crown ether compound is open chain crown ether, benzo-crown ether, cycloalkyl any one in crown ether or any multiple mixture.
6. the extraction agent as described in claim 4 or 5, is characterized in that: described crown ether compound is dibenzo-18 crown-6.
7. the extraction agent as described in any one of claim 4-6, is characterized in that: in this extraction agent, and the volume ratio of sec-butyl acetate and phenyl ethyl ether is 1:0.2-0.5, and
The volume mass of sec-butyl acetate and crown ether compound is than being 1:0.002-0.008 ml/g.
8. the extraction agent as described in any one of claim 4-7, it is characterized in that: in this extraction agent, the volume ratio of sec-butyl acetate and phenyl ethyl ether is 1:0.2-0.5, and the volume mass of sec-butyl acetate and crown ether compound ratio is 1:0.002-0.008 ml/g, and also need satisfied following condition: phenyl ethyl ether is 1:0.006-0.012 ml/g with the volume mass ratio of crown ether compound.
9. the purposes of the extraction agent described in any one of claim 1-8 in coal chemical industrial waste water phenol removal.
10. one kind uses the dephenolization method of the coal chemical industrial waste water of extraction agent described in any one of claim 1-8.
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