CN1834040A - Extraction and dephenolization process of coal gasification wastewater - Google Patents
Extraction and dephenolization process of coal gasification wastewater Download PDFInfo
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- CN1834040A CN1834040A CN 200610033936 CN200610033936A CN1834040A CN 1834040 A CN1834040 A CN 1834040A CN 200610033936 CN200610033936 CN 200610033936 CN 200610033936 A CN200610033936 A CN 200610033936A CN 1834040 A CN1834040 A CN 1834040A
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Abstract
This invention discloses a method to remove high-concentration hydroxybenzenes from coal-gasification sewage, that is, coal-gasification sewage containing hydroxybenzenes and isobutyl methyl ketone as extracting solvent are mixed and separated so as to obtain solvent phase and remnant aqueous phase liquid. Solvent and crude hydroxybenzene are extracted from the solvent phase by distillation. Multiple-class reflux extraction is carried out towards remnant aqueous phase liquid and rudimental solvent is further extracted from the extract. Facilities involved in this method include a static mixer, an oil-water separator, a hydroxybenzene distillation tower and an extraction tower. Extracting coal-gasification sewage containing high-concentration hydroxybenzenes with the method provided by this invention, total hydroxybenzene extraction ratio can be as high as 92%. Besides, it also has the advantages of simple technique, soft conditions and recyclable extraction solution.
Description
Technical field
The present invention relates to a kind of processing recovery method of waste water, particularly a kind of high density contains the method for extracting and dephenolizing of phenol coal gasification waste water.
Background technology
Phenols is a prototype matter poisonous substance, to all toxic effect of all life individualities.Content is extremely low still can to cause chronic poisoning, can directly cause biological death when concentration is higher than 1mg/L, serious harm ecology and environment.Gasification, oil refining and coking industry produce a large amount of phenolic wastewater in process of production, and waste water quality is very complicated, phenol concentration height, and phenol is of a great variety, and existing unit phenol has polyphenol again; Water quality is middle meta-alkalescence; Contain organism such as lipid acid, ketone and amine, sour gas, tar, flyash etc. in addition.Waste water COD
CrValue is high, and is difficult to biological degradation.The north certain coal gasification plant every production 10,000 m for example
3Coal gas, just produces 10t and contain the coal gasification waste water of phenol amount, and wherein polyphenol content reaches 1500～3500mg/L up to 4500～7000mg/L.Like this,, will produce about 800,000 t high-concentration phenolic wastewaters every year, and might cause serious water to pollute the Jiang Hai lake for the resident of medium-sized city that one 4,000,000 population is provided uses coal gas.This class high density contains the great technical barrier that the phenol trade effluent is China environmental protection and waste water treatment always.The dephenolize abstraction technique of developing such waste water can reduce the phenol content of waste water on the one hand significantly, reduces the pollution to environment; Valuable material in the recoverable wastewater fully utilizes on the other hand.
The method that reclaims phenol in the high-concentration phenolic wastewater has solvent extration, absorption method, steam blow-off method, ion exchange method, chemical precipitation, reverse osmosis method etc.Solvent extration is to utilize the solubleness of phenol in organic solvent greater than the solubleness in water, thereby the phenol extraction in the waste water is come out.Extensively all use both at home and abroad in a large number in solvent extration dephenolize efficient height, extraction agent source.But contain the extracting and dephenolizing of phenol gasification, oil refining and coke-oven waste water for high density, the subject matter that exists has at present: (1) common extraction agent is low to the extraction efficiency of the phenolic wastewater of meta-alkalescence and polyphenol; (2) heightening efficiency is low; (3) extraction equipment easily stops up etc.
Ionization takes place in aldehydes matter hardly under acidic conditions, exist with molecularity.And in the basic solution when pH＞8, phenol begins to take place ionization (is example with phenol): PhOHf PhO
-+ H
+, when pH＞9, it is more obvious to dissociate.The PhO of ionic state
-The group wetting ability strengthens, and the solubleness in water increases substantially, thereby causes effect of extracting to descend.And the polyphenol in the waste water is because polyhydric effect, and it is water-soluble bigger than unit phenol, also is difficult to effective extraction usually.
Harbin Gas Works adopts diisopropyl ether as extraction agent, this factory's gasification phenolic wastewater is carried out extracting and dephenolizing handle.Diisopropyl ether has boiling point and saturation steam forces down, water-soluble little, reclaim easily, advantage such as power consumption is little, but its dephenolize, particularly polyphenol efficient is low.Total phenol concentration is still up to about 1400mg/L in the waste water after the dephenolize, and wherein polyphenol just has 800～1100mg/L, COD
CrAbout value 6000mg/L.Not only cause the waste of phenol, and this waste water enters follow-up biochemical treatment tank, seriously exceed the biochemical treatment load, be difficult to reach the sewage discharge index request, basin, downstream, Song Hua River water body is caused serious threat.Diisopropyl ether can meet the demands substantially to the effect of extracting of unit phenol, but is not a kind of good extraction agent for polyphenol, and its partition ratio is very low.Diisopropyl ether Pyrogentisinic Acid's partition ratio is 36.5, but Resorcinol and hydroxyquinol have only 1.03 and 0.18 respectively, and is not suitable as the extraction solvent of the coal gasification waste water that contains polyphenol.In addition, the turntable extracting tower efficient that this factory now uses is lower, and through on-site proving, the actual effect of extracting that has only about 0.9～1.2 grade can not satisfy actual requirement.
Melanism group coke-oven plant, Heilungkiang has the complicated phenolic wastewater of a large amount of compositions to produce in coking and recovery coke chemicals process, contains volatile phenol and non-volatile phenol, prussiate, ammonia, sulfide and tar etc.This factory uses light benzene as extraction agent, and the dephenolize extraction efficiency is low.Light benzene is volatile, poisonous, and is bigger to human body harm.Now this factory uses N instead, N-two (1-methyl-heptyl) ethanamide (N503)/diesel oil is as extraction agent, although this extraction agent efficient is higher, loss is low, toxicity is little, phenol, alkali, heat there are stability preferably, but because N503 is difficult for layering, the foam floor height in complexation extraction, produce emulsion, thereby cause the solvent entrainment loss serious, increase the extraction cost, effect is not satisfactory in practical application in industry.
South China Science ﹠ Engineering University once adopted tributyl phosphate (TBP)/kerosin that the high concentrated base slag of China Petrochemical Industry's Guangzhou Branch refinery is contained the phenol refinery water to have carried out the complexometric extraction dephenolize.Under certain processing condition, the volatile phenol concentration of waste water can be dropped to below the 50mg/L by 10767mg/L, effect of extracting is pretty good.But the regeneration of TBP need be used in the alkali lye and the complexometric extraction thing, generates the sodium salt of phenol in the process, reclaims the subsequent treatment process complexity of phenol, is difficult to be applied to the big situation of wastewater flow rate.
In sum, the extracting and dephenolizing technology of high-concentration phenolic wastewater is not satisfactory at present, and the phenol concentration of processed waste water is still quite high, is difficult to satisfy the qualified discharge of follow-up biochemical treatment, the severe contamination surrounding enviroment.
Summary of the invention
The present invention is directed to the problem that prior art exists, the method for extracting and dephenolizing that provides a kind of high density to contain the phenol coal gasification waste water makes in the phenolic wastewater aldehydes matter effectively be deviate from and reclaim.
The method for extracting and dephenolizing that high density of the present invention contains the phenol coal gasification waste water comprises the steps:
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution;
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting;
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling.
Can also comprise the steps:
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1) and recycles.
Preferred version of the present invention is as follows:
In the described step (1), containing the phenol coal gasification waste water is that phenol content is 3000～10000mg/L, volatile phenol content 1500～4000mg/L; The pH value is 5～10.5, COD
CrValue is 15000～30000mg/L, and the waste water that contains lipid acid, tar, coal ash.
In the step (1), described mixing is adopted static mixer to carry out and is flowed mixing, mixeding liquid temperature is 30～85 ℃, and containing phenol coal gasification waste water pH value in the mixed solution is 3～11, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 10～10: 1 with the volume ratio that contains the phenol coal gasification waste water.
In the step (1), the filler that described static mixer uses can be the honeycomb structured packing, and the described extraction tower of step (3) is a packing tower, and the filler of its use is the honeycomb structured packing.
In the step (2), described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 10～40min.Be preferably 15～25min.
In the step (3), described rectifying adopts rectifying tower to carry out.
In the step (4), described extraction adopts extraction tower to carry out the extraction of 3～8 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), its initial total phenol content is less than 50mg/L, extraction solvent is 1: 10～10: 1 with the volume ratio (comparing) of surplus liquid, and extraction temperature is 30～85 ℃, and extraction pH value is 3～11.
Wherein extraction solvent be preferably 1: 8 with the volume ratio (comparing) of surplus liquid～1: 2, extraction temperature is preferably 40～60 ℃, extraction pH value is preferably 5～10, extracts progression and is preferably 4～6 grades.The selection of above-mentioned extraction parameter, the reasons are as follows:
(1) when extraction pH value is 3～11, the extraction solvent methyl iso-butyl ketone (MIBK) is not subjected to the influence of pH variation substantially to the extraction ability of phenol, and effect of extracting is good; When pH＞11, the phenol extraction effect reduces; PH＞12 o'clock then very difficult the phenol that from waste water, extracts.Contain and contain a large amount of free ammonias in the phenol coal gasification waste water, waste water is middle meta-alkalescence, can satisfy the requirement of extraction pH value.
(2) change of extraction temperature can make that extraction equilibrium is moved, and changes the extraction equilibrium constant, thereby influences effect of extracting.When extraction temperature was 30～85 ℃, temperature variation was not obvious to the influence of this extraction agent dephenolize, considered actual plant effluent temperature, preferred 40～60 ℃ of extraction temperature.
(3) extraction solvent influences extraction tower sum of series raffinate waste water phenol concentration mutually with the selection of the volume ratio (comparing) of described surplus liquid, also influences the process cost of solvent reclamation simultaneously.In separation requirement one regularly, compare greatly more, the progression of required extraction tower equipment is low more, and cost of equipment reduces, but the solvent reclamation expense increases.Therefore, compare under the situation that satisfies technology (phenol concentration) and equipment index (extraction progression), the smaller the better usually, so the volume ratio (comparing) of extraction solvent and described surplus liquid is 1: 10～10: 1 in the inventive method, preferred 1: 8～1: 2.
(4) comparing 1: 8～1: 2, when the initial total phenol content of extraction solvent is not more than 50mg/L, adopting the solvent methyl iso-butyl ketone (MIBK) by the extraction of 3～8 stage countercurrents, can the total phenol concentration in the waste water dropped to below the 400mg/L, volatile phenol concentration drops to about 10mg/L.But along with the increase of extraction progression, the amplitude that phenol concentration reduces is more and more littler, increases extraction progression after progression arrives 8 grades again, can not effectively reduce the concentration of phenol, can increase cost on the contrary,, be preferably 4～6 grades so the extraction progression in the inventive method is 3～8 grades.
Adopt the inventive method to handle high density and contain the phenol coal gasification waste water, can realize that total phenol removal rate reaches 92%, the decreasing ratio of volatile phenol reaches 99%, COD
CrDecreasing ratio about 85%.This method has reclaimed the aldehydes matter in the waste water effectively, and the aldehydes matter of recovery is the rectifying purifying further, is converted into useful industrial chemicals.
Compared with prior art, method of the present invention has following advantage:
(1) the dephenolize extraction solvent of method employing of the present invention is to the partition ratio height of phenolic compound, particularly for the extraction of polyphenol, solve the problem that general extraction solvent can not effectively extract polyphenol, be particularly suitable for the processing that height is dense, contain the coal gasification waste water of multiple phenol, the inclined to one side neutral and alkali of water quality.
(2) method and technology technology of the present invention is simple, and mild condition need not to add acid and regulates the waste water potential of hydrogen before the extraction, and the solvent after the extraction can adopt rectification method regeneration.
(3) equipment of method employing of the present invention has very strong anti-blocking, is suitable for containing the coal gasification waste water of flyash, tar.
(4) method dephenolize efficient height of the present invention.Total phenol removal rate in the waste water reaches 92%, and the decreasing ratio of volatile phenol reaches 99%, COD
CrDecreasing ratio is about 85%, can reclaim the aldehydes matter in the waste water effectively, also helps the follow-up governance for reaching standard discharging of waste water.
Embodiment
Embodiment 1
Select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 3000mg/L, volatile phenol content 4000mg/L; The pH value is 5, COD
CrValue is 30000mg/L, oil content 200mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and mixeding liquid temperature is 30 ℃, and containing phenol coal gasification waste water pH value in the mixed solution is 11, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 10 with the volume ratio that contains the phenol coal gasification waste water.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 40min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 3 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 10: 1, and extraction temperature is 30 ℃, and extraction pH value is 11.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1) and recycles.
Waste water total phenol content after the processing is less than 420mg/L, and wherein volatile phenol is less than 20mg/L; COD
CrBe about 3800mg/L, decreasing ratio reaches 92.2%, 99.3%, 82.7% respectively.
Embodiment 2
Select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 10000mg/L, volatile phenol content 1500mg/L; The pH value is 10.5, COD
CrValue is 15000mg/L, oil content 500mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and mixeding liquid temperature is 85 ℃, and containing phenol coal gasification waste water pH value in the mixed solution is 3, and the extraction solvent methyl iso-butyl ketone (MIBK) is 10: 1 with the volume ratio that contains the phenol coal gasification waste water.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 10min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 8 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 1: 10, and extraction temperature is 85 ℃, and extraction pH value is 3.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1).
Total phenol content in the processed waste water is less than 400mg/L, and wherein volatile phenol is less than 15mg/L; COD
CrBe about 3600mg/L, decreasing ratio reaches 92.6%, 99.3%, 83.6% respectively.
Embodiment 3
Select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 5000mg/L, volatile phenol content 2500mg/L; The pH value is 6.5, COD
CrValue is 25000mg/L, oil content 300mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and mixeding liquid temperature is 45 ℃, and containing phenol coal gasification waste water pH value in the mixed solution is 8, and the extraction solvent methyl iso-butyl ketone (MIBK) is 10: 7 with the volume ratio that contains the phenol coal gasification waste water.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 30min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 5 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 1: 7, and extraction temperature is 65 ℃, and extraction pH value is 6.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1).
Total phenol content in the processed waste water is less than 450mg/L, and wherein volatile phenol is less than 20mg/L; COD
CrBe about 4200mg/L, decreasing ratio reaches 91.7%, 99.3%, 80.9% respectively.
Embodiment 4
Select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 9000mg/L, volatile phenol content 3500mg/L; The pH value is 6.5, COD
CrValue is 19000mg/L, oil content 400mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and mixeding liquid temperature is 80 ℃, and containing phenol coal gasification waste water pH value in the mixed solution is 10, and the extraction solvent methyl iso-butyl ketone (MIBK) is 10: 3 with the volume ratio that contains the phenol coal gasification waste water.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 35min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 3～8 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 10: 3, and extraction temperature is 45 ℃, and extraction pH value is 5.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1) and recycles.
Total phenol content in the processed waste water is less than 350mg/L, and wherein volatile phenol is less than 10mg/L; COD
CrBe about 3500mg/L, decreasing ratio reaches 93.5%, 99.6%, 84.1% respectively.
Embodiment 5
Select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 3000mg/L, volatile phenol content 4000mg/L; The pH value is 5, COD
CrValue is 30000mg/L, oil content 200mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and described mixeding liquid temperature is 40 ℃, and the pH value that contains the phenol coal gasification waste water in the mixed solution is 11, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 8 with containing phenol coal gasification waste water volume ratio.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 25min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 4 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 1: 2, and extraction temperature is 40 ℃, and extraction pH value is 10.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1).
Total phenol content in the processed waste water is less than 320mg/L, and wherein volatile phenol is less than 10mg/L; COD
CrBe about 3300mg/L, decreasing ratio reaches 94.1%, 99.6%, 85.0% respectively.
Embodiment 6
Select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 10000mg/L, volatile phenol content 1500mg/L; The pH value is 10.5, COD
CrValue is 15000mg/L, oil content 500mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and described mixeding liquid temperature is 60 ℃, and the pH value that contains the phenol coal gasification waste water in the mixed solution is 5, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 2 with the volume ratio that contains the phenol coal gasification waste water.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 15min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 6 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 1: 8, and extraction temperature is 60 ℃, and extraction pH value is 5.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1).
Total phenol content in the processed waste water is less than 400mg/L, and wherein volatile phenol is less than 10mg/L; COD
CrBe about 3700mg/L, decreasing ratio reaches 92.6%, 99.6%, 83.2% respectively.
Embodiment 7
(1) select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 3000mg/L, volatile phenol content 1500mg/L; The pH value is 10.5, COD
CrValue is 30000mg/L, oil content 200mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and described mixeding liquid temperature is 60 ℃, and the pH value that contains the phenol coal gasification waste water in the mixed solution is 11, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 8 with containing phenol coal gasification waste water volume ratio.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 15min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 6 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 1: 2, and extraction temperature is 40 ℃, and extraction pH value is 5.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1).
Total phenol content in the processed waste water is less than 380mg/L, and wherein volatile phenol is less than 10mg/L; COD
CrBe about 3700mg/L, decreasing ratio reaches 93%, 99.6%, 83.2% respectively.
Embodiment 8
(1) select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 10000mg/L, volatile phenol content 4000mg/L; The pH value is 5, COD
CrValue is 15000mg/L, oil content 500mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and described mixeding liquid temperature is 60 ℃, and the pH value that contains the phenol coal gasification waste water in the mixed solution is 5, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 8 with the volume ratio that contains the phenol coal gasification waste water.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 25min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 4 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 1: 8, and extraction temperature is 60 ℃, and extraction pH value is 10.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1).
Waste water total phenol content after the processing is less than 420mg/L, and wherein volatile phenol is less than 20mg/L; COD
CrBe about 3800mg/L, decreasing ratio reaches 92.2%, 99.3%, 82.7% respectively.
Embodiment 9
(1) select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 10000mg/L, volatile phenol content 4000mg/L; The pH value is 5, COD
CrValue is 15000mg/L, oil content 500mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and described mixeding liquid temperature is 40 ℃, and the pH value that contains the phenol coal gasification waste water in the mixed solution is 5, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 2 with the volume ratio that contains the phenol coal gasification waste water.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 25min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 4 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 1: 2, and extraction temperature is 40 ℃, and extraction pH value is 10.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1) and recycles.
Total phenol content in the processed waste water is less than 420mg/L, and wherein volatile phenol is less than 20mg/L; COD
CrBe about 3800mg/L, decreasing ratio reaches 92.2%, 99.3%, 82.7% respectively.
Embodiment 10
Select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 8000mg/L, volatile phenol content 3000mg/L; The pH value is 9.5, COD
CrValue is 25000mg/L, oil content 4mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and described mixeding liquid temperature is 60 ℃, and the pH value that contains the phenol coal gasification waste water in the mixed solution is 11, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 8 with containing phenol coal gasification waste water volume ratio.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 25min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 6 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 1: 8, and extraction temperature is 40～60 ℃, and extraction pH value is 10.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1).
Total phenol content in the processed waste water is less than 450mg/L, and wherein volatile phenol is less than 20mg/L; COD
CrBe about 4000mg/L, decreasing ratio reaches 93.1%, 99.5%, 85.7% respectively.
Embodiment 11
Select the pending phenol coal gasification waste water that contains, treatment capacity is 100t/h, and phenol content is 10000mg/L, volatile phenol content 4000mg/L; The pH value is 5, COD
CrValue is 30000mg/L, oil content 500mg/L
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution; Described mixing is adopted static mixer to carry out and is flowed mixing, and described mixeding liquid temperature is 40 ℃, and the pH value that contains the phenol coal gasification waste water in the mixed solution is 11, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 2 with containing phenol coal gasification waste water volume ratio.
(2), obtain solvent phase and surplus liquid with the mixed solution phase-splitting; Described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 25min.
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling; Described extraction adopts extraction tower to carry out the extraction of 4 stage countercurrents, and extraction solvent is a methyl iso-butyl ketone (MIBK), and its initial total phenol content is less than 50mg/L, and the volume ratio of extraction solvent and surplus liquid is 1: 8, and extraction temperature is 60 ℃, and extraction pH value is 10.
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1).
Total phenol content in the processed waste water is less than 310mg/L, and wherein volatile phenol is less than 10mg/L; COD
CrBe about 2900mg/L, decreasing ratio reaches 90.3%, 99.4%, 80.7% respectively.
Among the embodiment, GB GB 7491-87 bromination volumetry is adopted in the volatile phenol concentration determination.
Direct bromination method is adopted in total phenol concentration determination.In detected water sample, add excessive bromine, make aldehydes matter and bromine generate brominated phenol, excessive bromine iodometric titrationiodimetry titration, thus calculate total phenol content.This method can be measured phenol nearly all in the waste water, is applicable to the big coal gasification waste water of many, the non-volatile phenol amounts of phenol kind that contains of the present invention.
Claims (9)
1. a method for extracting and dephenolizing that contains the phenol coal gasification waste water is characterized in that comprising the steps:
(1) will contain the phenol coal gasification waste water mixes with the extraction solvent methyl iso-butyl ketone (MIBK) and obtains mixed solution;
(2), obtain the surplus liquid of solvent phase and water with the mixed solution phase-splitting;
(3) extraction solvent and crude phenols are reclaimed in the solvent phase rectifying that step (2) is obtained;
(4) the surplus liquid of water that obtains of step (2) obtains being rich in phenol extraction solvent and raffinate again through multi-stage counter current extraction, and raffinate is carried out residual extraction solvent recycling.
2, method according to claim 1 is characterized in that also comprising the steps:
(5) extraction solvent that obtains of extraction solvent that step (3) is obtained and step (4) returns step (1) and recycles.
3, method according to claim 1 and 2 is characterized in that in the described step (1), and containing the phenol coal gasification waste water is that phenol content is 3000～10000mg/L, volatile phenol content 1500～4000mg/L; The pH value is 5～10.5, COD
CrValue is 15000～30000mg/L, and the waste water that contains lipid acid, tar, coal ash.
4. method according to claim 3, it is characterized in that in the step (1), described mixing is adopted static mixer to carry out and is flowed mixing, 30～85 ℃ of mixeding liquid temperatures, contain phenol coal gasification waste water pH value 3～11 in the mixed solution, the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 10～10: 1 with the volume ratio that contains the phenol coal gasification waste water.
5, method according to claim 4, it is characterized in that in the step (1), described mixeding liquid temperature is 40～60 ℃, and the pH value that contains the phenol coal gasification waste water in the mixed solution is 5～11, and the extraction solvent methyl iso-butyl ketone (MIBK) is 1: 8～1: 2 with the volume ratio that contains the phenol coal gasification waste water.
6. method according to claim 5 is characterized in that in the step (2), and described phase-splitting adopts water-and-oil separator to carry out, and described mixed solution residence time in water-and-oil separator is 10～40min.
7, method according to claim 6 is characterized in that in the step (2) that described mixed solution residence time in water-and-oil separator is 15～25min.
8. method according to claim 7, it is characterized in that in the step (4), described extraction adopts extraction tower to carry out the extraction of 3～8 stage countercurrents, extraction solvent is a methyl iso-butyl ketone (MIBK), its initial total phenol content is less than 50mg/L, the volume ratio of extraction solvent and surplus liquid is 1: 10～10: 1, and extraction temperature is 30～85 ℃, and extraction pH value is 3～11.
9, method according to claim 8, it is characterized in that in the step (4), described extraction adopts extraction tower to carry out the extraction of 4～6 stage countercurrents, extraction solvent is a methyl iso-butyl ketone (MIBK), its initial total phenol content is less than 50mg/L, the volume ratio of extraction solvent and surplus liquid is 1: 8～1: 2, and extraction temperature is 40～60 ℃, and extraction pH value is 5～10.
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