CN101597092A - Single tower alkali injection pressurization stripping is handled the method for coal gasification wastewater - Google Patents
Single tower alkali injection pressurization stripping is handled the method for coal gasification wastewater Download PDFInfo
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Abstract
The invention discloses a kind of single tower alkali injection pressurization stripping and handle the method for coal gasification wastewater.This method comprises divides hot and cold two bursts of chargings to enter Dan Ta from sewage stripping tower top and middle and upper part coal gasification wastewater, get the high density ammonia from single tower side line extraction gas ammonia through three grades of fractional condensation, lime set is returned head tank, annotate alkali with upper/lower positions so that fixedly ammonium is converted into ammonia and removes at side line, the alkali lye mass percent concentration is 20%～40%, consumption is not higher than in the waste water the fixedly mole number of ammonium, and extraction still liquid advances the follow-up extracting and dephenolizing process of coal gasification wastewater at the bottom of the tower.The present invention realizes that coal gasification wastewater removes sour gas, free ammonium and the fixing process of ammonium simultaneously in the sewage stripping tower, obtain the high density ammonia, tower still purify waste water middle carbonic acid gas, hydrogen sulfide, free ammonium and fixedly ammonium content is extremely low, less scaling, the pH value is reduced to about 6, for good extraction conditions is created in the follow-up solvent extraction dephenolize of coal gasification wastewater.The present invention is applicable to coal gasification wastewater and comprehensive treating process process thereof.
Description
Technical field
The present invention relates to the processing recovery method of coal gasification wastewater, particularly a kind of single tower alkali injection pressurization stripping is handled the method for coal gasification wastewater.
Background technology
Gasification is the effective means that clean and effective utilizes coal, is widely used in the industry such as gas maked coal, synthetic ammonia, coal power generation.Lurgi pressure gasification technology is to use one of maximum gasifying process at present, and coal gas can produce the sewage of a large amount of complicated components in washing, cooling, scavenging process, and owing to contains the COD and the NH of higher concentration
3-N, and make the difficult problem in the water treatment of being treated as of this type of sewage, and become one of primary pollution source of water surrounding along with the gasification industrial expansion.The gas sewage complicated component contains multiple inorganic pollutant such as ammonia, sulfate radical, carbonate, cyanogen root etc., and wherein ammonia content is the highest, also contains multiple organic substance such as phenolic compound, lipid acid, tar, ketone and amine etc.For such sewage, the mode that generally adopts the chemical separating flow process to combine with biochemical treatment is handled both at home and abroad.Chemical separating comprises unit processes such as depickling, extraction, deamination, solvent recuperation, to remove sour gas, reclaims phenol, ammonia etc.Sewage enters extracting tower and removes CO after removing tar and part light oil through pre-treatment such as flash distillation, sedimentations
2, H
2Sour gas such as S enter the extraction tower extracting and dephenolizing then.Extraction solvent generally adopts diisopropyl ether.Sewage after the extraction carries out biochemical treatment through entering biochemical treatment workshop section after deamination and the solvent recuperation again.The promising dephenolization effect of shortcoming that this flow process is the most outstanding is bad at present, and the easy fouling of equipment is stopped up serious.
Single tower pressurization stripping is that commercial runs such as refining of petroleum, petrochemical complex produce one of effective treatment process of sour water.U.S. Pat 3518167 and Chinese invention patent 90107237.0,98114341.5 propose single tower stripping side line respectively and extract the method for handling sour water out, by the stripping tower top hydrogen sulfide of purifying, the middle part of the tower ammonia of purifying, hydrogen sulfide and the ammonia in the stripping sewage is come in the bottom of tower.In the coal gasification wastewater field, Chinese patent 200610036072.7 discloses the method and apparatus that a kind of single tower pressurization stripping is handled coal gasification wastewater, take stripping depickling deamination at coal gasification waste water, three steps of extracting and dephenolizing and solvent recuperation, improve the decreasing ratio of carbonic acid gas and ammonia, thereby the pH value that reduces extraction is improved dephenolization effect, but this patented technology is not considered the fixedly existence of ammonium, fixedly ammonium is owing to contain thiocyanate in the coal gasification wastewater, thiosulfate anion, nitrate radical, nitrite anions, sulfate radical, the cyanogen root, inferior sulfate radical and other fatty acid materials, easy and ammonium root forms fixedly ammonium, the method that this technology is difficult to adopt pyrolytic decomposition fixedly ammonium removes, and single tower comes out purify waste water in fixedly ammonium content surpass the water quality standard of follow-up biochemical treatment, influence biochemical treatment.
Summary of the invention
The objective of the invention is to the defective at prior art, the fixedly ammonium in a kind of effective elimination sewage is provided, the single tower alkali injection pressurization stripping that makes it to satisfy follow-up biochemical processing requirements is handled the method for coal gasification wastewater.
Purpose of the present invention is achieved through the following technical solutions:
A kind of single tower alkali injection pressurization stripping is handled the method for coal gasification wastewater, and the coal gasification wastewater of carbonated, hydrogen sulfide, ammonia and phenol is divided into cold raw water and hot charge water two-way; Cold raw water enters the packing section top of stripping tower cat head after cooling, tower top pressure is 0.2～0.6MPa, and 40～52.3 ℃ of temperature are carried out ammonia and absorbed; Hot charge water enters the hot feed inlet on tower tray section top, stripping tower middle part behind heat exchange to 140～155 ℃; Cold feed will be joined with hot feed after will absorbing ammonia, carry out heat exchange at steam with the rising of tower still, ammonia, carbonic acid gas and hydrogen sulfide stripping are come out, and carbonic acid gas and hydrogen sulfide sour gas are discharged by cat head, and described cold raw water and hot charge water weight ratio are 0.1～1: 1; 2-8 piece column plate position is injected alkali lye pressurization back in the stripping Tata under side line ammonia gas mixture extraction mouth, and the alkali lye mass percent concentration is 20%～40%, and the alkali lye molar weight is not higher than in the waste water the fixedly mole number of ammonium, and fixedly ammonium is converted into ammonia and removes; Contain the ammonia gas mixture and extract out from stripping tower middle part tower tray section side line ammonia gas mixture extraction mouth, get the high density ammonia through three grades of fractional condensation, lime set is returned head tank, and the head tank tower bottom pressure is 0.25～0.64MPa, 120～165 ℃ of temperature; Column bottom temperature provides heat for whole stripping tower, sour gas in the vaporize water and ammonia; The coal gasification wastewater that purifies is discharged back continuation extracting and dephenolizing at the bottom of tower.
The described ammonia gas mixture that contains is the extraction gas mixture that contains ammonia, water vapour, carbonic acid gas and phenol.
The described ammonia gas mixture weight that contains accounts for 8～15% of hot and cold raw water gross weight.
Described three grades of fractional condensation get the high density ammonia and are meant by three grades of alternating temperature transformations generation gas ammonias, the working pressure of one-level partial condenser is 0.4～0.5MPa, service temperature is 110～140 ℃, the working pressure of secondary partial condenser is 0.35～0.4MPa, 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 ℃.
The present invention compared with prior art has following advantage:
(1) the inventive method is compared Chinese patent 200610036072.7, and the fixedly ammonium by in the method effective elimination sewage of annotating alkali satisfies follow-up biochemical processing requirements, also reduces ammonia still facility investment and working cost commonly used in the common coal gasification wastewater.
(2) the chemical industry treatment process that generally adopts of the relative gasification industry of the inventive method has improved CO
2With the decreasing ratio of ammonia, can be with the CO in original coal gasification wastewater flow process
2Residual quantity is by 2000mgL
-1About be reduced to 300mgL
-1Below, total ammonia content is reduced to 300mgL
-1Below, thereby alleviate ammonium salt crystallization and scale problems in original flow process.
(3) employing of the inventive method makes the tower still pH value of purifying waste water be reduced to about 6, thereby improve extraction solvent dephenolization effect subsequently greatly, the pollution load of handling back sewage descends significantly, alleviates the processing load of biochemical section, solves the improvement difficult problem of high density phenol-containing wastewater.
Description of drawings
Fig. 1 is a kind of typical process principle process that single tower alkali injection pressurization stripping of the present invention is handled coal gasification wastewater.Among the figure: 1-gasification raw material sewage, 2-raw material water tank, 3-raw material water pump, 4-cold feed water-to-water heat exchanger, 5-sewage stripping tower, 6-hot feed first-class heat exchanger, 7-hot feed secondary heat exchanger (one-level condensate cooler), three grades of interchanger of 8-hot feed, 9-clarified water pump, 10-purifies waste water, 11-sour gas, 12-one-level partial condenser, 13-B-grade condensation water cooler, 14-secondary partial condenser, 15-phlegma water cooler, three grades of condensate coolers of 16-, three grades of partial condensers of 17-, the thick ammonia of 18-, 19-reboiler, 20-steam, 21-leads directly to steam, the 22-steam condensate, 23-alkali lye, 24-annotates alkali pump.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is further described, need to prove, embodiment does not constitute the restriction to the claimed scope of the present invention.
As shown in Figure 1, the stripping tower 5 that single tower alkali injection pressurization stripping is handled the coal gasification wastewater device is divided into three sections, and top is packing section, and middle part and bottom are the tower tray section, and cat head to hot charge water inlet is a packing section, and random packing is housed, and is used for ammonia and absorbs; Hot charge water inlet to side line ammonia gas mixture extraction mouth is a middle part tower tray section, is used for the carbonic acid gas stripping; Side line ammonia gas mixture is adopted and is exported at the bottom of the tower is bottom tower tray section, is used for the ammonia stripping.The raw material access to plant comprises raw material water tank 2, raw material water pump 3, feed water interchanger 4, hot feed first-class heat exchanger 6, hot feed secondary heat exchanger (also being the one-level condensate cooler) 7, three grades of interchanger 8 of hot feed and annotates alkali pump 24; Raw material water tank 2 is connected with raw material water pump 3, and raw material water pump 3 is connected with the packing section top of stripping tower 5 through feed water interchanger 4, is the cold feed pipeline; Raw material water pump 3 also is connected with the hot feed inlet of stripping tower 5 through hot feed first-class heat exchanger 6, three grades of interchanger 8 of hot feed secondary heat exchanger 7 and hot feed successively, is the hot feed pipeline; Annotate alkali pump 24 and be connected with stripping tower 5, for adding the alkali pipeline in side line ammonia gas mixture extraction mouth lower end.Clarified water pump 9 one ends are connected with at the bottom of stripping tower 5 towers, and three grades of interchanger 8 of the other end and hot feed are connected, and three grades of interchanger 8 of hot feed also are connected with hot feed first-class heat exchanger 6, purify waste water 10 will enter next the extraction workshop section.Steam-pipe is connected with reboiler 19 with at the bottom of stripping tower 5 towers respectively, and reboiler 19 is connected with stripping tower 5 bottom tower tray sections.The side line ammonia gas mixture extraction mouth of stripping tower 5 is connected with three grades of partial condensers 17 with one-level partial condenser 12, B-grade condensation water cooler 13, secondary partial condenser 14, three grades of fractional condensation water coolers 16 successively through hot feed secondary heat exchanger (also being the one-level condensate cooler) 7, phlegma water cooler 15 1 ends are connected with secondary partial condenser 14 with one-level partial condenser 12 respectively, the other end is connected with raw material water tank 2, and three grades of partial condensers 17 also are connected with incoming stock water pot.
Embodiment 1
The gasification raw material sewage 1 of carbonated, hydrogen sulfide, ammonia and phenol, flow is 89.1t/hr, total ammonia is 5104mg/L (wherein fixedly ammonium is 870mg/L), gas concentration lwevel is 2309mg/L, hydrogen sulfide is 81mg/L, the pH value is 10.5, total phenol content is 6500mg/L, incoming stock water pot 2, after raw material water pump 3 pressurization, be to be divided into two burst chargings at 1: 4 to enter stripping tower 5 by the ratio of the cold raw material water yield and hot charge water yield weight, cold raw water charging enters the packing section top of stripping tower cat head behind cold feed water-to-water heat exchanger 4, make tower top temperature remain 46.5 ℃; The charging of another strand hot charge water is purified waste water, after side line extracts gas heat exchange to 150.1 ℃ out, is entered the hot feed inlet of stripping tower middle part tower tray section through hot feed first-class heat exchanger 6, hot feed secondary heat exchanger (also being the one-level condensate cooler) 7, three grades of interchanger of hot feed 8 and tower still; The mode that the tower still utilizes reboiler 19 and straight-through steam 21 (steam 20 is divided into two strands, and one advances reboiler 19, and another strand is straight-through steam 21) to combine, making tower bottom pressure is 0.64MPa, 162.2 ℃ of temperature; Hot feed is met at the bottom of the tower behind the rising steam, the ammonia in the charging, H
2S and CO
2Come out to move by stripping to cat head.After running into the cat head cold feed, ammonia is dissolved in rapidly in the water, move down with liquid phase, and ammonium salts such as the sulphur hydrogenation ammonium in the cold liquid feeding, bicarbonate of ammonia decomposes owing to temperature raises gradually in moving downward process, discharge H
2S and CO
2Change gas phase over to.After the tower middle part forms rich ammonia gas, contains gas mixtures extractions such as ammonia, water vapour and carbonic acid gas, adopt three grades of condensations, improve ammonia concentration step by step.At the 3rd block of column plate in side line ammonia gas mixture extraction mouth lower end is that 20% alkali lye 23 injects in the tower with 380kg/hr flow velocity pressurization back by annotating alkali pump 24 with mass percent concentration, and fixedly ammonium is converted into ammonia and removes; Cat head goes out sour gas 11; Purify waste water at the bottom of the tower by clarified water pump 9, through after three grades of interchanger 8 of hot feed, the hot feed first-class heat exchanger 6 heat exchange cooling, be cooled to 40～60 ℃ of temperature and advance the follow-up extracting and dephenolizing of the coal gasification wastewater stage again by pipeline 10.Containing the ammonia gas mixture extracts out from sewage stripping tower 5 middle part tower tray section side line ammonia gas mixture extraction mouths, through obtaining the thick ammonia 18 that concentration is higher than 90 volume % behind hot feed secondary heat exchanger (one-level condensate cooler) 7, one-level partial condenser 12, B-grade condensation water cooler 13, secondary partial condenser 14, three grades of fractional condensation water coolers 16, three grades of partial condensers 17, thick ammonia 18 is delivered to the ammonia refining system; The branch lime set that one-level partial condenser 12 and secondary partial condenser produce merges incoming stock water pot 2 by the branch lime set of phlegma water cooler 15 cooling backs and three grades of partial condensers 17.
The treatment process of embodiment 2～3 is with embodiment 1, and processing parameter sees Table 1; Comparative example 4 is the comparative example, and processing parameter sees Table 1.
Table 1
| Numbering | 1 | 2 | 3 | Comparative example 4 |
| The raw material water yield, t/hr | 89.1 | 60.0 | 82.3 | 62.5 |
| Tower bottom pressure, MPa | 0.64 | 0.53 | 0.57 | 0.55 |
| Tower top temperature, ℃ | 46.5 | 52.3 | 40.4 | 40.0 |
| Column bottom temperature, ℃ | 162.2 | 158.4 | 155.0 | 153.0 |
| The hot feed temperature, ℃ | 150.1 | 149.6 | 150.3 | 140.0 |
| The cold feed temperature, ℃ | 41.2 | 38.2 | 39.7 | 39.6 |
| Side line extraction amount, w% | 8％ | 12％ | 10％ | 11％ |
| Cold and hot charge ratio | 1∶4 | 1∶4 | 2∶5 | 1∶4 |
| Annotate alkali number (20%), kg/hr | 380 | 420 | 350 | 0 |
| The first partial condenser temperature, ℃ | 128 | 119 | 130 | 121 |
| The first partial condenser pressure, MPa | 0.45 | 0.50 | 0.45 | 0.48 |
| The second partial condenser temperature, ℃ | 90 | 85 | 92 | 90 |
| The second partial condenser pressure, MPa | 0.35 | 0.38 | 0.35 | 0.36 |
| The 3rd partial condenser temperature, ℃ | 36 | 38 | 41 | 42 |
| The 3rd partial condenser pressure, MPa | 0.20 | 0.26 | 0.32 | 0.20 |
| Raw material water quality, free ammonia, mg/L | 4234 | 14633 | 9460 | 12610 |
| Fixed ammonia, mg/L | 870 | 756 | 720 | 810 |
| CO 2，mg/L | 2309 | 2309 | 2309 | 2309 |
| H 2S，mg/L | 81 | 125 | 100 | 111 |
| pH | 10.5 | 10.9 | 10.6 | 11.0 |
| Tower still water quality, free ammonia, mg/L | 50 | 20 | 30 | 50 |
| Fixed ammonia, mg/L | 180 | 260 | 220 | 730 |
| CO 2，mg/L | 220 | 740 | 650 | 970 |
| H 2S，mg/L | Do not detect | - | - | - |
| pH，mg/L | 6.5 | 5.4 | 6.0 | 5.7 |
| Thick ammonia is formed NH 3，％ | 95 | 93 | 98 | 97 |
| CO 2，％ | 2 | 1 | 0.5 | 0.8 |
| Steam consumption quantity, kg/t sewage | 180.2 | 145.1 | 160.8 | 155.5 |
Comparative example 4 is not for adding the running example under the alkali situation, do not add alkali as can be seen from Table 1 and only relies on the high temperature at the bottom of the tower to be difficult to fixedly ammonium is wherein removed.Fixedly ammonium is too high will make follow-up biochemical treatment be difficult to go on, and wish all that generally fixedly ammonium is reduced to below the 300mg/L.1～3 of embodiment is by adding the mode of alkali, can with CN
-, SCN
-, Cl
-Etc. the form bonded fixedly ammonium adopt the chemical reaction mode to be converted into free ammonium to remove away, fixedly ammonium content is 180～260mg/L, much smaller than the 730mg/L of comparative example 4, the effect highly significant.It can also be seen that from embodiment 1～3, good more when alkali number increases gradually to the removal effect of fixing ammonium, but the maximum mole number that alkali number needs will with waste water in fixedly the mole number of ammonium equate.
Claims (4)
1, a kind of single tower alkali injection pressurization stripping is handled the method for coal gasification wastewater, and the coal gasification wastewater of carbonated, hydrogen sulfide, ammonia and phenol is divided into cold raw water and hot charge water two-way; Cold raw water enters the packing section top of stripping tower cat head after cooling, tower top pressure is 0.2～0.6MPa, and 40～52.3 ℃ of temperature are carried out ammonia and absorbed; Hot charge water enters the hot feed inlet on tower tray section top, stripping tower middle part behind heat exchange to 140～155 ℃; Cold feed will be joined with hot feed after will absorbing ammonia, carry out heat exchange at steam with the rising of tower still, ammonia, carbonic acid gas and hydrogen sulfide stripping are come out, and carbonic acid gas and hydrogen sulfide sour gas are discharged by cat head, and described cold raw water and hot charge water weight ratio are 0.1～1: 1; It is characterized in that: 2-8 piece column plate position is injected alkali lye pressurization back in the stripping Tata under side line ammonia gas mixture extraction mouth, the alkali lye mass percent concentration is 20%～40%, the alkali lye molar weight is not higher than in the waste water the fixedly mole number of ammonium, and fixedly ammonium is converted into ammonia and removes; Contain the ammonia gas mixture and extract out from stripping tower middle part tower tray section side line ammonia gas mixture extraction mouth, get the high density ammonia through three grades of fractional condensation, lime set is returned head tank, and the head tank tower bottom pressure is 0.25～0.64MPa, 120～165 ℃ of temperature; Column bottom temperature provides heat for whole stripping tower, sour gas in the vaporize water and ammonia; The coal gasification wastewater that purifies is discharged back continuation extracting and dephenolizing at the bottom of tower.
2, method according to claim 1 is characterized in that: the described ammonia gas mixture that contains is the extraction gas mixture that contains ammonia, water vapour, carbonic acid gas and phenol.
3, method according to claim 2 is characterized in that: the described ammonia gas mixture weight that contains accounts for 8～15% of hot and cold raw water gross weight.
4, method according to claim 1, it is characterized in that: described three grades of fractional condensation get the high density ammonia and are meant by three grades of alternating temperature transformations generation gas ammonias, the working pressure of one-level partial condenser is 0.4～0.5MPa, service temperature is 110～140 ℃, the working pressure of secondary partial condenser is 0.35～0.4MPa, service temperature is 70～105 ℃, and the working pressure of three grades of partial condensers is 0.2～0.35MPa, and service temperature is 30～50 ℃.
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