CN102674608A - Method for recycling and treating high-concentration phenol/ammonia wastewater - Google Patents
Method for recycling and treating high-concentration phenol/ammonia wastewater Download PDFInfo
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Abstract
The invention discloses a method for recycling and treating high-concentration phenol/ammonia wastewater. The method mainly comprises the following steps of: performing saturable absorption on the high-concentration phenol/ammonia wastewater from which suspended matter and tar are removed by using acidic gas; reducing the pH value of the wastewater, and inputting the wastewater into an extraction tower for performing continuous countercurrent extraction; deacidifying and deaminizing extracted raffinate phases by a single tower pressurization steam stripping process, and performing steam stripping on solvent; alkalifying at a sidetrack by using an acid water stripper; ejecting acid gas phases and extraction agents from the top of the stripper, and obtaining ammonia gas from the lower sidetrack through three-level segregation; and inputting the extracted raffinate phases into a rectifying phenol tower, recovering the extraction agent, and thus obtaining by-product crude phenol. The acidic gas used in the method is produced in the wastewater treatment process, and is internally circulated to fulfill the aims of energy saving and environmental protection; deacidification, deamination and stream stripping of solvent can be realized in the single tower steam stripping process, the high-concentration phenol/ammonia wastewater can be effectively treated, the crude phenol and the ammonia can be simultaneously recovered, effluent can meet the requirement of subsequent conventional biochemical treatment, and the final wastewater confirms to the standard and is drained.
Description
Technical field
The invention belongs to the coal gasification waste water process field.The chemical industry treatment process that relates to the phenol ammonia waste water is specifically related to a kind of high-concentration phenol and ammonia Wastewater Recovery treatment process.
Background technology
The shortage of water resources has become one of stern challenge of face of mankind nowadays.China is the country of a rich coal resources; Coal chemical industry enterprises is more, reclaims process such as refining in coal coking, gas purification and Chemicals and has produced a large amount of trade effluents, must in time handle; Be recycled, alleviate the pressure that current water scarcity and environmental pollution bring.The water-quality constituents of coal gasification waste water is complicated, and Pollutant levels are high.Usually the heterogeneous ring compound that contains a large amount of ammonia nitrogens, aldehydes matter, mononuclear aromatics and polycyclic aromatic hydrocarbons and nitrogenous, sulphur, oxygen also has part tar and prussiate.In the processing of actual phenolic wastewater, to the phenolic wastewater of high density, at first considered is recycled phenol; Phenol concentration is lower to containing, the waste water of no recovery value or after recycling, still leave the waste water of remaining phenol, then must carry out harmless treatment, accomplishes qualified discharge, to realize the unification of economic benefit and environmental benefit.
To the processing of high-concentration phenol ammonia waste water, lean on physics and chemical process to be difficult to reach emission standard merely, need several kinds of different treatment method synthesis to use the mode that adopts the chemical separating pretreatment process to combine usually with biochemical treatment.Remove the part lime-ash through unit such as deposition, extraction, strippings, oils etc. reclaim valuable material phenol ammonia, send biochemical treatment then.Existing flow process mainly comprises two big types of the SX dephenolizes again of deamination and the depickling again of depickling, extracting and dephenolizing, deamination.
Chinese patent 201010227835.2 has proposed a kind of treatment process of phenolic wastewater in smashed coal pressure gasification; This patent is to the depickling phenolic wastewater, and through the washing of carbonic acid gas washing tower, the saturated back of acid gas gets into extraction tower and carries out extracting and dephenolizing; Waste water after the dephenolize flows out the back with being pumped into the ammonia recycle section from the extraction tower bottom; But contain a large amount of sour gas and a small amount of extraction agent in the waste water, do not consider to remove, and directly get into the ammonia recycle section.Chinese patent 201010292208.7 is same to adopt the carbonic acid gas saturated absorptions earlier, extracting and dephenolizing again, and the waste water after the dephenolize removes sour gas and ammonia through the pressurization stripping; Waste water is delivered to the solvent stripping tower and is reclaimed solvent at the bottom of single Tata; But in the single tower process of pressurization, tower still temperature has made the extraction agent in the water evaporate up for 120 ~ 170 ℃, overflows from single tower side line and cat head; Therefore; It is unreasonable aspect single tower stripping depickling deamination and the recovery of solvent stripping to pressurize in its main flow process, and adopts DIPE extremely low to polyphenol extraction partition ratio, and the processed waste water total phenol content is undesirable.
Summary of the invention
The objective of the invention is to deficiency, a kind of high-concentration phenol and ammonia Wastewater Recovery treatment process is provided to prior art.
To achieve these goals, the present invention has adopted following technical scheme:
A kind of high-concentration phenol and ammonia Wastewater Recovery treatment process may further comprise the steps:
(1) sour gas saturated absorption
With the high-concentration phenol ammonia waste water controlled temperature of removing suspended substance, tar is 30 ~ 70 ℃; Get in the tower from acid gas absorption tower top; Sour gas gets into from the bottom, absorption tower; By sour gas the high-concentration phenol ammonia waste water is carried out saturated absorption, the phenol ammonia waste water pH value that sour gas is saturated is controlled to be 7 ~ 8 backs and gets into extraction tower; Sour gas can be recycled after discharging from the top, absorption tower;
(2) SX dephenolize
The phenol ammonia waste water that sour gas after step (1) is handled is saturated gets in the extraction tower from extraction tower top, carries out continuous countercurrent extraction with the extraction agent that gets into from the extraction tower bottom, and extraction temperature is 40 ~ 80 ℃; The volume ratio of phenol ammonia waste water and extraction agent is (4 ~ 8): 1; Extraction phase after the extraction gets into rectifier unit phenol tower and reclaims solvent, and extracting phase gets into depickling deamination and solvent stripping workshop section;
(3) single tower pressurization stripping carries out depickling deamination and solvent stripping
Adopt single tower pressurization stripping to carry out depickling deamination and solvent stripping simultaneously; Specifically comprise: the extracting phase that step (2) is obtained is divided into hot and cold two bursts of chargings entering sour water stripping (SWS) tower; Tower still temperature is 130 ~ 170 ℃, and tower still pressure is 0.3 ~ 0.7MPa, and the cold feed temperature is 40 ~ 80 ℃; Hot feed is 120 ~ 155 ℃, and hot and cold charge ratio is 1: (2 ~ 5); Sour water stripping (SWS) tower side line adds alkali, and cat head is discharged gas phase and extraction agent, and the water outlet of tower still gets into biochemical treatment workshop section;
The top side line is extracted gas phase out after cooling, oily water separation, and extraction agent recycles, and phlegma gets into waste water tank or the sour water stripping (SWS) tower carries out the dephenolize deamination, and the solvent behind the dephenolize deamination is recycled recovery; The bottom side line obtains ammonia and sends into the ammonia refining system after three grades of fractional condensation; One-level partial condenser working pressure is 0.3 ~ 0.5MPa; Service temperature is 110 ~ 140 ℃, and the working pressure of secondary partial condenser is 0.28 ~ 0.4MPa, and service temperature is 70 ~ 105 ℃; The working pressure of three grades of partial condensers is 0.2 ~ 0.35MPa, and service temperature is 30 ~ 50 ℃;
(4) solvent recuperation
The extraction phase that step (2) is obtained gets into phenol tower rectifying separation extraction agent and crude phenols, and the tower still temperature of rectifying phenol tower is 190 ~ 220 ℃, and working pressure is 0.1 ~ 0.2MPa, reflux ratio 0.2 ~ 0.8, and the extraction agent recycle after the separation, crude phenols are as sub product.
In the step of the present invention (1); The sour gas that uses in the said acid gas absorption tower is as producing in the wastewater treatment process; Only when the initial unlatching of device, need extra introducing; Device move successfully back sour gas circulating inside, and concrete recycle circuit is: the part entering acid gas absorption tower of the sour gas that is produced by the sour water stripping (SWS) column overhead, rest part entering boiler or emission-control equipment.
In the step (1), said sour gas is carbonic acid gas and/or hydrogen sulfide.
In the step of the present invention (2), said extraction agent is DIPE, hexone or TAME.
In the step of the present invention (3), add sodium hydroxide solution or sodium carbonate solution when said side line adds alkali, the mass concentration of said sodium hydroxide solution or sodium carbonate solution is 15 ~ 50%.
In the step (3); The sour water stripping (SWS) column overhead is discharged in the gas phase and is contained sour gas, water vapour, ammonia and extraction agent; Through cooling, oily water separation; The oil phase extraction agent recycles, and the part circulation of sour gas gets into acid gas absorption tower, and rest part gets into boiler or emission-control equipment.
In the step (3), sour water stripping (SWS) tower top side line is extracted out in the gas phase and is mainly contained sour gas, water vapour, ammonia and extraction agent, after overcooling, oily water separation, and the recycle of oil phase extraction agent, phlegma gets into waste water tank or circulation receipt tower.
In the step (3), sour water stripping (SWS) tower bottom side line is extracted out in the gas phase and is mainly contained sour gas, water vapour, ammonia and extraction agent, and after three grades of fractional condensation, it is refining that the vapor phase ammonia pneumatic transmission is gone into ammonia, and phlegma gets into waste water tank or circulation receipt tower.
The present invention compared with prior art has the following advantages and beneficial effect:
(1) is different from the special carbonic acid gas saturated absorption high-concentration phenol ammonia waste water that uses in the conventional art; Sour gas that the present invention uses is as producing in the wastewater treatment process; Only when the initial unlatching of device, need extra introducing; Device move successfully sour gas circulating inside afterwards, can make into that the waste water ph of extraction tower is lower than 8, is the good acid or alkali environment of SX creation;
(2) according to high-concentration phenol and ammonia waste water quality situation, select different extraction agents, it is low to contain polyphenol content; Select DIPE; Selection hexone or TAME that polyphenol content is high, and the extraction agent consumption is few, and solvent almost all reclaims in theory;
(3) adopt single tower to add to calm the anger to carry and realize that cat head goes out sour gas and extraction agent, side line goes out extraction agent and ammonia respectively, and biochemistry is directly advanced in the water outlet of tower still, and this multifunctional single tower makes flow process more succinct, has the function of extracting tower, deammoniation tower, water tower simultaneously;
(4) sour gas that comes out of single top of tower is after the separating and extracting agent, and the circulation of part sour gas gets into sour gas saturated absorption tower, and all the other advance boiler or other devices reclaim;
(5) waste water among the present invention only need experience and once heat up and a temperature-fall period, and heat-exchange system is more succinct, and energy consumption is lower;
(6) method of the present invention not only can effectively be removed phenol, ammonia and sour gas in the waste water, and other organic pollutant content in the waste water also can reduce greatly, and COD is lower than 3000mgL
-1, and the pH value of final outflow water is reduced to about 7.
Description of drawings
Fig. 1 is the employed device synoptic diagram of high-concentration phenol and ammonia Wastewater Recovery treatment process of the present invention.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is done and to further describe.But the scope that the present invention requires to protect is not limited thereto.
The high-concentration phenol and ammonia Wastewater Recovery treatment unit that the present invention adopts is as shown in Figure 1, mainly comprises: acid gas absorption tower 1, extraction tower 2, solvent tank 3; Rectifying phenol tower 4, sour water stripping (SWS) tower 5, acid gas separating tank 6; Gun barrel 7, one-level flash tank 8, two-stage flash jar 9 and three grades of flash tanks 10.
High-concentration phenol ammonia waste water 11 gets into from the top of acid gas absorption tower 1, and with sour gas 15 counter-current absorption that get into from acid gas absorption tower 1 bottom, from driving sour gas 12, all the other periods come from acid gas separating tank 6 to sour gas when driving.The waste water 27 that comes out from the acid gas absorption tower bottom gets into from extraction tower 2 tops, and always carries out continuous countercurrent extraction from solvent tank 3, the extraction agent 28 that gets into from extraction tower 2 bottoms.Extraction tower 2 top extraction phases 29 get into rectifying phenol tower 4 through heat exchange, and the cat head gas phase 30 of rectifying phenol tower is after cooling, and extraction agent loops back solvent tank, is partly refluxed to rectifying phenol tower, and the tower still of rectifying phenol tower gets crude phenols sub product 17.Extraction tower 2 lower part outlet waste water 31 minutes cold and hot two strand 32 and 33 entering sour water stripping (SWS) towers 5, the tower still water outlet 26 of sour water stripping (SWS) tower 5 gets into biochemical section after cooling.The side line of sour water stripping (SWS) tower 5 has the alkali of adding pipeline 18.The cat head gas phase 34 of sour water stripping (SWS) tower 5 gets into acid gas separating tank 6 after cooling; Sour gas 35 part circulation disacidify property absorption column of gas 1; All the other 21 remove boiler or Acidic Gas Treating device, and the phlegma 36 of acid gas separating tank 6 gets into gun barrels 7 further oily water separations and isolates extraction agent 16 and water 37.Sour water stripping (SWS) tower 5 top side lines 19 are after the heat exchange cooling; Also get into gun barrel 7 and isolate extraction agent 16 and water 37; Gun barrel 7 isolated extraction agent 16 recycles desolvate jars 3, and water 37 mixes waste water tank or time sour water stripping (SWS) tower 4 with the phlegma 25 of fractional condensation system.The bottom side line 20 of sour water stripping (SWS) tower 5 behind one-level flash tank 8, two-stage flash jar 9, three grades of flash tanks 10 ammonia 24 and phlegma 25; Ammonia 24 further deammoniations are refining, and phlegma 25 is mixed into waste water tank or returns sour water stripping (SWS) tower 4 with the water 37 that comes out from gun barrel 7.
Sour gas absorption tower 1 is the material filling type extraction tower, and extraction tower 2 is rotating disc type extraction tower or material filling type extraction tower, and rectifying phenol tower 4 is a tray column with sour water stripping (SWS) tower 5.
Embodiment 1
85 tons/hour of 37 ℃ of phenol ammonia waste water flows, total phenol content 5599mgL
-1, polyphenol content 1980mgL wherein
-1, ammonia 7975mgL
-1, carbonic acid gas 5000mgL
-1, hydrogen sulfide 1000mgL
-1, pH value 9.3.Feed acid gas absorption tower, regulating phenol ammonia waste water pH value is that 7.2 backs get into extraction tower; Extraction tower is the material filling type extraction tower, and extraction agent is a hexone, 40 ℃ of extraction temperature, and waste water extraction agent volume ratio is 4:1, the extraction phase after the extraction gets into the phenol tower and reclaims solvent, 210 ℃ of tower stills, 118 ℃ of cats head, working pressure 0.18MPa, reflux ratio 0.2; Extracting phase is divided into hot and cold two bursts of chargings and gets into sour water stripping (SWS) tower, 56 ℃ of tower top temperatures, 160 ℃ of tower still temperature; Tower still pressure 0.6MPa, hot and cold charge ratio is 1:3,40 ℃ of cold feed temperature; 150 ℃ of hot feed temperature; Sour water stripping (SWS) tower side line adds alkali, and cat head is discharged gas phase and extraction agent, and the water outlet of tower still gets into biochemical treatment workshop section;
The top side line is extracted gas phase extraction agent recycle after cooling, oily water separation out; The bottom side line is after three grades of fractional condensation; It is refining to get the further ammonia of 85% (wt.) ammonia, and one-level partial condenser working pressure is 0.5MPa, and service temperature is 140 ℃; The working pressure of secondary partial condenser is 0.4MPa; Service temperature is 90 ℃, and the working pressure of three grades of partial condensers is 0.35MPa, and service temperature is 50 ℃.
Total phenol 220 mgL in the waste water after the processing
-1, total ammonia 312 mgL
-1, sour gas is a trace, COD is 2140 mgL
-1
Embodiment 2
85 tons/hour of 37 ℃ of phenol ammonia waste water flows, total phenol content 5599mgL
-1, polyphenol content 1980mgL wherein
-1, ammonia 7975mgL
-1, carbonic acid gas 5000mgL
-1, hydrogen sulfide 1000mgL
-1, pH value 9.3.Feed acid gas absorption tower, utilizing acid gas absorption tower to regulate phenol ammonia waste water pH value is that 8.0 backs get into extraction tower; Extraction tower is the material filling type extraction tower, and extraction agent is a TAME, 40 ℃ of extraction temperature, and waste water extraction agent volume ratio is 7:1, the extraction phase after the extraction gets into the phenol tower and reclaims solvent, 220 ℃ of tower stills, 87 ℃ of cats head, working pressure 0.12MPa, reflux ratio 0.8; Extracting phase is divided into hot and cold two bursts of chargings and gets into sour water stripping (SWS) tower, 50 ℃ of tower top temperatures, 170 ℃ of tower still temperature; Tower still pressure 0.7MPa, hot and cold charge ratio is 1:3,40 ℃ of cold feed temperature; 155 ℃ of hot feed temperature; Sour water stripping (SWS) tower side line adds alkali, and cat head is discharged gas phase and extraction agent, and the water outlet of tower still gets into biochemical treatment workshop section;
The top side line is extracted extraction agent recycle after cooling, oily water separation out; The bottom side line is after three grades of fractional condensation; It is refining to get the further ammonia of 90% (wt.) ammonia, and one-level partial condenser working pressure is 0.4MPa, and service temperature is 110 ℃; The working pressure of secondary partial condenser is 0.35MPa; Service temperature is 70 ℃, and the working pressure of three grades of partial condensers is 0.2MPa, and service temperature is 30 ℃.
Total phenol 320 mgL in the waste water after the processing
-1, total ammonia 268 mgL
-1, sour gas is a trace, COD is 2490 mgL
-1
85 tons/hour of 92 ℃ of phenol ammonia waste water flows, total phenol content 5140mgL
-1, polyphenol content 1800mgL wherein
-1, ammonia 8500mgL
-1, carbonic acid gas 4500mgL
-1, hydrogen sulfide 80mgL
-1, pH value 10.1.Waste water cools and feeds acid gas absorption tower after 55 ℃ to utilize acid gas absorption tower to regulate phenol ammonia waste water pH value be 8.0 back entering extraction towers; Extraction tower is the material filling type extraction tower, and extraction agent is a hexone, 58 ℃ of extraction temperature, and waste water extraction agent volume ratio is 5.5:1, the extraction phase after the extraction gets into the phenol tower and reclaims solvent, 210 ℃ of tower stills, 119 ℃ of cats head, working pressure 0.1MPa, reflux ratio 0.5; Extracting phase is divided into hot and cold two bursts of chargings and gets into sour water stripping (SWS) tower, 48 ℃ of tower top temperatures, 165 ℃ of tower still temperature; Tower still pressure 0.65MPa, hot and cold charge ratio is 1:3,58 ℃ of cold feed temperature; 140 ℃ of hot feed temperature; Sour water stripping (SWS) tower side line adds alkali, and cat head is discharged gas phase and extraction agent, and the water outlet of tower still gets into biochemical treatment workshop section;
The top side line is extracted extraction agent recycle after cooling, oily water separation out; The bottom side line is after three grades of fractional condensation; It is refining to get the further ammonia of 82% (wt.) ammonia, and one-level partial condenser working pressure is 0.45MPa, and service temperature is 128 ℃; The working pressure of secondary partial condenser is 0.35MPa; Service temperature is 90 ℃, and the working pressure of three grades of partial condensers is 0.2MPa, and service temperature is 36 ℃.
Total phenol 240 mgL in the waste water after the processing
-1, total ammonia 298 mgL
-1, sour gas is a trace, COD is 2230 mgL
-1
Embodiment 4
85 tons/hour of 60 ℃ of phenol ammonia waste water flows, unit phenol content 5550mgL
-1, ammonia 8500mgL
-1, carbonic acid gas 4500mgL
-1, hydrogen sulfide 80mgL
-1, pH value 9.8.Feed acid gas absorption tower, utilizing acid gas absorption tower to regulate phenol ammonia waste water pH value is that 7.8 backs get into extraction tower; Extraction tower is the rotating disc type extraction tower, and extraction agent is a DIPE, 60 ℃ of extraction temperature, and waste water extraction agent volume ratio is 4:1, the extraction phase after the extraction gets into the phenol tower and reclaims solvent, 190 ℃ of tower stills, 68 ℃ of cats head, working pressure 0.2MPa, reflux ratio 0.6; Extracting phase is divided into hot and cold two bursts of chargings and gets into sour water stripping (SWS) tower, 55 ℃ of tower top temperatures, 130 ℃ of tower still temperature; Tower still pressure 0.3MPa, hot and cold charge ratio is 1:3,60 ℃ of cold feed temperature; 120 ℃ of hot feed temperature; Sour water stripping (SWS) tower side line adds alkali, and cat head is discharged gas phase and extraction agent, and the water outlet of tower still gets into biochemical treatment workshop section;
The top side line is extracted extraction agent recycle after cooling, oily water separation out; The bottom side line is after three grades of fractional condensation; 75% (wt.) ammonia further to advance ammonia refining, one-level partial condenser working pressure is 0.3MPa, service temperature is 110 ℃; The working pressure of secondary partial condenser is 0.28MPa; Service temperature is 90 ℃, and the working pressure of three grades of partial condensers is 0.1MPa, and service temperature is 30 ℃.
Phenol 186 mgL in unit in the waste water after the processing
-1, total ammonia 350 mgL
-1, sour gas is a trace, COD is 2983 mgL
-1
85 tons/hour of 92 ℃ of phenol ammonia waste water flows, total phenol content 5140mgL
-1, polyphenol content 1800mgL wherein
-1, ammonia 8500mgL
-1, carbonic acid gas 4500mgL
-1, hydrogen sulfide 80mgL
-1, pH value 10.1.Waste water cools and after 70 ℃, feeds acid gas absorption tower, and utilizing acid gas absorption tower to regulate phenol ammonia waste water pH value is that 8.0 backs get into extraction tower; Extraction tower is the material filling type extraction tower, and extraction agent is a TAME, 72 ℃ of extraction temperature, and waste water extraction agent volume ratio is 5.5:1, the extraction phase after the extraction gets into the phenol tower and reclaims solvent, 210 ℃ of tower stills, 88 ℃ of cats head, working pressure 0.15MPa, reflux ratio 0.5; Extracting phase is divided into hot and cold two bursts of chargings and gets into sour water stripping (SWS) tower, 48 ℃ of tower top temperatures, 165 ℃ of tower still temperature; Tower still pressure 0.65MPa, hot and cold charge ratio is 1:5,72 ℃ of cold feed temperature; 150 ℃ of hot feed temperature; Sour water stripping (SWS) tower side line adds alkali, and cat head is discharged gas phase and extraction agent, and the water outlet of tower still gets into biochemical treatment workshop section;
The top side line is extracted extraction agent recycle after cooling, oily water separation out; The bottom side line is after three grades of fractional condensation; It is refining to get the further ammonia of 82% (wt.) ammonia, and one-level partial condenser working pressure is 0.43MPa, and service temperature is 127 ℃; The working pressure of secondary partial condenser is 0.35MPa; Service temperature is 89 ℃, and the working pressure of three grades of partial condensers is 0.12MPa, and service temperature is 32 ℃.
Total phenol 264mgL in the waste water after the processing
-1, total ammonia 310 mgL
-1, sour gas is a trace, COD is 2642 mgL
-1
100 tons/hour of 92 ℃ of phenol ammonia waste water flows, total phenol content 5140mgL
-1, polyphenol content 1800mgL wherein
-1, ammonia 8500mgL
-1, carbonic acid gas 4500mgL
-1, hydrogen sulfide 80mgL
-1, pH value 10.1.Waste water cools and after 70 ℃, feeds acid gas absorption tower, and utilizing acid gas absorption tower to regulate phenol ammonia waste water pH value is that 7.4 backs get into extraction tower; Extraction tower is the material filling type extraction tower, and extraction agent is a hexone, 80 ℃ of extraction temperature, and waste water extraction agent volume ratio is 8:1, the extraction phase after the extraction gets into the phenol tower and reclaims solvent, 210 ℃ of tower stills, 116 ℃ of cats head, working pressure 0.17MPa, reflux ratio 0.8; Extracting phase is divided into hot and cold two bursts of chargings and gets into sour water stripping (SWS) tower, 86 ℃ of tower top temperatures, 170 ℃ of tower still temperature; Tower still pressure 0.7MPa, hot and cold charge ratio is 1:5,80 ℃ of cold feed temperature; 155 ℃ of hot feed temperature; Sour water stripping (SWS) tower side line adds alkali, and cat head is discharged gas phase and extraction agent, and the water outlet of tower still gets into biochemical treatment workshop section;
The top side line is extracted extraction agent recycle after cooling, oily water separation out; The bottom side line is after three grades of fractional condensation; It is refining to get the further ammonia of 82% (wt.) ammonia, and one-level partial condenser working pressure is 0.5MPa, and service temperature is 140 ℃; The working pressure of secondary partial condenser is 0.4MPa; Service temperature is 105 ℃, and the working pressure of three grades of partial condensers is 0.35MPa, and service temperature is 50 ℃.
Total phenol 334 mgL in the waste water after the processing
-1, total ammonia 189 mgL
-1, sour gas is a trace, COD is 2746 mgL
-1
Claims (8)
1. a high-concentration phenol and ammonia Wastewater Recovery treatment process is characterized in that, may further comprise the steps:
(1) sour gas saturated absorption
With the high-concentration phenol ammonia waste water controlled temperature of removing suspended substance, tar is 30 ~ 70 ℃; Get in the tower from acid gas absorption tower top; Sour gas gets into from the bottom, absorption tower; By sour gas the high-concentration phenol ammonia waste water is carried out saturated absorption, the phenol ammonia waste water pH value that sour gas is saturated is controlled to be 7 ~ 8 backs and gets into extraction tower; Sour gas can be recycled after discharging from the top, absorption tower;
(2) SX dephenolize
The phenol ammonia waste water that sour gas after step (1) is handled is saturated gets in the extraction tower from extraction tower top, carries out continuous countercurrent extraction with the extraction agent that gets into from the extraction tower bottom, and extraction temperature is 40 ~ 80 ℃; The volume ratio of phenol ammonia waste water and extraction agent is (4 ~ 8): 1; Extraction phase after the extraction gets into rectifier unit phenol tower and reclaims solvent, and extracting phase gets into depickling deamination and solvent stripping workshop section;
(3) single tower pressurization stripping carries out depickling deamination and solvent stripping
Adopt single tower pressurization stripping to carry out depickling deamination and solvent stripping simultaneously; Specifically comprise: the extracting phase that step (2) is obtained is divided into hot and cold two bursts of chargings entering sour water stripping (SWS) tower; Tower still temperature is 130 ~ 170 ℃, and tower still pressure is 0.3 ~ 0.7MPa, and the cold feed temperature is 40 ~ 80 ℃; Hot feed is 120 ~ 155 ℃, and hot and cold charge ratio is 1: (2 ~ 5); Sour water stripping (SWS) tower side line adds alkali, and cat head is discharged gas phase and extraction agent, and the water outlet of tower still gets into biochemical treatment workshop section;
The top side line is extracted gas phase out after cooling, oily water separation, and extraction agent recycles, and phlegma gets into waste water tank or the sour water stripping (SWS) tower carries out the dephenolize deamination, and the solvent behind the dephenolize deamination is recycled recovery; The bottom side line obtains ammonia and sends into the ammonia refining system after three grades of fractional condensation; One-level partial condenser working pressure is 0.3 ~ 0.5MPa; Service temperature is 110 ~ 140 ℃, and the working pressure of secondary partial condenser is 0.28 ~ 0.4MPa, and service temperature is 70 ~ 105 ℃; The working pressure of three grades of partial condensers is 0.2 ~ 0.35MPa, and service temperature is 30 ~ 50 ℃;
(4) solvent recuperation
The extraction phase that step (2) is obtained gets into phenol tower rectifying separation extraction agent and crude phenols, and the tower still temperature of rectifying phenol tower is 190 ~ 220 ℃, and working pressure is 0.1 ~ 0.2MPa, reflux ratio 0.2 ~ 0.8, and the extraction agent recycle after the separation, crude phenols are as sub product.
2. recovery and treatment method according to claim 1; It is characterized in that in the step (1), the sour gas that uses in the said acid gas absorption tower is as producing in the wastewater treatment process; Only when the initial unlatching of device, need extra introducing; Device move successfully back sour gas circulating inside, and concrete recycle circuit is: the part entering acid gas absorption tower of the sour gas that is produced by the sour water stripping (SWS) column overhead, rest part entering boiler or emission-control equipment.
3. recovery and treatment method according to claim 2 is characterized in that, in the step (1), said sour gas is carbonic acid gas and/or hydrogen sulfide.
4. recovery and treatment method according to claim 3 is characterized in that, in the step (2), said extraction agent is DIPE, hexone or TAME.
5. recovery and treatment method according to claim 4 is characterized in that, in the step (3), adds sodium hydroxide solution or sodium carbonate solution when said side line adds alkali, and the mass concentration of said sodium hydroxide solution or sodium carbonate solution is 15 ~ 50%.
6. according to the described recovery and treatment method of one of claim 1 ~ 5; It is characterized in that in the step (3), the sour water stripping (SWS) column overhead is discharged in the gas phase and contained sour gas, water vapour, ammonia and extraction agent; Through cooling, oily water separation; The oil phase extraction agent recycles, and the part circulation of sour gas gets into acid gas absorption tower, and rest part gets into boiler or emission-control equipment.
7. recovery and treatment method according to claim 6; It is characterized in that; In the step (3), sour water stripping (SWS) tower top side line is extracted out in the gas phase and is mainly contained sour gas, water vapour, ammonia and extraction agent, after overcooling, oily water separation; The recycle of oil phase extraction agent, phlegma gets into waste water tank or circulation receipt tower.
8. recovery and treatment method according to claim 7; It is characterized in that; In the step (3), sour water stripping (SWS) tower bottom side line is extracted out in the gas phase and is mainly contained sour gas, water vapour, ammonia and extraction agent, after three grades of fractional condensation; It is refining that the vapor phase ammonia pneumatic transmission is gone into ammonia, and phlegma gets into waste water tank or circulation receipt tower.
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| CN2012101451377A CN102674608A (en) | 2012-05-11 | 2012-05-11 | Method for recycling and treating high-concentration phenol/ammonia wastewater |
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| CN2012101451377A CN102674608A (en) | 2012-05-11 | 2012-05-11 | Method for recycling and treating high-concentration phenol/ammonia wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN103496812A (en) * | 2013-09-29 | 2014-01-08 | 河南龙成煤高效技术应用有限公司 | Method for treating high-concentration phenol-ammonia wastewater |
| CN103570172A (en) * | 2013-10-24 | 2014-02-12 | 天华化工机械及自动化研究设计院有限公司 | Phenol-ammonia coal gasification sewage treatment method |
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| CN103964543A (en) * | 2014-05-06 | 2014-08-06 | 河南龙成煤高效技术应用有限公司 | Method for oil and phenol removal from wastewater in field of coal chemical industry |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597092A (en) * | 2009-01-09 | 2009-12-09 | 华南理工大学 | Single tower alkali injection pressurization stripping is handled the method for coal gasification wastewater |
| CN101870529A (en) * | 2010-07-12 | 2010-10-27 | 赛鼎工程有限公司 | Method for treating phenolic wastewater in smashed coal pressure gasification |
| CN102241453A (en) * | 2010-09-25 | 2011-11-16 | 仲恺农业工程学院 | Method for treating coal gasification wastewater containing phenol and ammonia |
| CN102259943A (en) * | 2011-07-21 | 2011-11-30 | 天津市昊永化工科技有限公司 | Energy-saving method for recycling wastewater containing phenol and ammonia |
| CN102336451A (en) * | 2011-06-17 | 2012-02-01 | 青岛君扬化工科技有限公司 | Coal chemical phenol-containing waste water dephenolization method |
| CN102351358A (en) * | 2011-06-30 | 2012-02-15 | 神华集团有限责任公司 | Method and system for treating phenol-containing acidic water by direct liquefaction with coal |
-
2012
- 2012-05-11 CN CN2012101451377A patent/CN102674608A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597092A (en) * | 2009-01-09 | 2009-12-09 | 华南理工大学 | Single tower alkali injection pressurization stripping is handled the method for coal gasification wastewater |
| CN101870529A (en) * | 2010-07-12 | 2010-10-27 | 赛鼎工程有限公司 | Method for treating phenolic wastewater in smashed coal pressure gasification |
| CN102241453A (en) * | 2010-09-25 | 2011-11-16 | 仲恺农业工程学院 | Method for treating coal gasification wastewater containing phenol and ammonia |
| CN102336451A (en) * | 2011-06-17 | 2012-02-01 | 青岛君扬化工科技有限公司 | Coal chemical phenol-containing waste water dephenolization method |
| CN102351358A (en) * | 2011-06-30 | 2012-02-15 | 神华集团有限责任公司 | Method and system for treating phenol-containing acidic water by direct liquefaction with coal |
| CN102259943A (en) * | 2011-07-21 | 2011-11-30 | 天津市昊永化工科技有限公司 | Energy-saving method for recycling wastewater containing phenol and ammonia |
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| CN102838249B (en) * | 2012-10-05 | 2014-02-19 | 上海会博新材料科技有限公司 | Device for treating filtrate generated in washing process of para-aramid resin |
| CN102838249A (en) * | 2012-10-05 | 2012-12-26 | 上海会博新材料科技有限公司 | Device for treating filtrate generated in washing process of para-aramid resin |
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| CN104628213A (en) * | 2013-11-07 | 2015-05-20 | 青岛博研达工业技术研究所(普通合伙) | Processing method of ammonia-containing tannery wastewater |
| CN103964543A (en) * | 2014-05-06 | 2014-08-06 | 河南龙成煤高效技术应用有限公司 | Method for oil and phenol removal from wastewater in field of coal chemical industry |
| CN103964543B (en) * | 2014-05-06 | 2016-01-27 | 河南龙成煤高效技术应用有限公司 | A kind of method of coal chemical technology waste water oil removing dephenolize |
| CN104147808A (en) * | 2014-07-29 | 2014-11-19 | 华南理工大学 | Dephenolizing extraction agent and application thereof |
| CN105152437A (en) * | 2015-07-14 | 2015-12-16 | 王庆元 | Online extraction and dephenolization method of coal tar wastewater |
| CN105417815A (en) * | 2015-11-06 | 2016-03-23 | 南京师范大学 | Method for treating salt-containing organic wastewater during production of cationic golden yellow dye X-GL |
| CN105565565A (en) * | 2015-12-15 | 2016-05-11 | 华南理工大学 | Method for treating highly-enriched phenol-containing coal chemical-industrial waste water by recycling efficient extraction agent |
| CN105712427B (en) * | 2016-04-05 | 2019-04-09 | 华南理工大学 | Polyphenol has the extractant and extracting process of high distribution coefficient in a kind of pair of phenol wastewater |
| CN107032555A (en) * | 2016-12-07 | 2017-08-11 | 赛鼎工程有限公司 | A kind of method for handling oil-containing coal gasification waste water |
| CN106554115A (en) * | 2016-12-08 | 2017-04-05 | 西安润格环保科技有限公司 | A kind of coal chemical industrial waste water is reduced pressure depickling deamination method and system step by step |
| CN106673289A (en) * | 2016-12-21 | 2017-05-17 | 华南理工大学 | Method and device for treating high-concentration organic phenol-containing coal gasification wastewater through enhanced extraction |
| CN108722139A (en) * | 2017-04-13 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of method and device of processing sour gas |
| CN108722139B (en) * | 2017-04-13 | 2020-11-10 | 中国石油化工股份有限公司 | Method and device for treating acid gas |
| CN108854165A (en) * | 2017-12-28 | 2018-11-23 | 郑州铂来化研科技有限公司 | Oily separation method in a kind of deammoniation tower ammonia lime set |
| CN110002629A (en) * | 2019-04-04 | 2019-07-12 | 中钢集团鞍山热能研究院有限公司 | A kind of the oil removing dephenolize combination treatment method and system of high-concentration phenol ammonia waste water |
| CN110002629B (en) * | 2019-04-04 | 2021-11-09 | 中钢集团鞍山热能研究院有限公司 | Oil and phenol removal combined treatment method and system for high-concentration phenol-ammonia wastewater |
| CN111847564A (en) * | 2019-04-28 | 2020-10-30 | 华南理工大学 | Semi-coke wastewater extraction dephenolization and negative pressure type extractant recovery method and device |
| CN110540329A (en) * | 2019-09-09 | 2019-12-06 | 陕西煤业化工集团神木天元化工有限公司 | Phenol-ammonia wastewater treatment method and system |
| CN112624466A (en) * | 2020-11-27 | 2021-04-09 | 陕西德信祥能源科技有限公司 | Coal chemical industry wastewater pretreatment method |
| CN112624477A (en) * | 2020-12-31 | 2021-04-09 | 天津同创恒泰科技有限公司 | Treatment device and treatment method for phenolic sodium salt decomposition wastewater |
| CN114873823A (en) * | 2022-06-10 | 2022-08-09 | 爱智环境科技(西安)有限公司 | Coking wastewater comprehensive treatment device and technological method |
| CN114873823B (en) * | 2022-06-10 | 2023-11-28 | 爱智环境科技(西安)有限公司 | Comprehensive treatment device and process method for coking wastewater |
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