CN101579603A - Process for advanced treatment of waste alkali in hydrogen sulfide removal - Google Patents
Process for advanced treatment of waste alkali in hydrogen sulfide removal Download PDFInfo
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- CN101579603A CN101579603A CNA200910087785XA CN200910087785A CN101579603A CN 101579603 A CN101579603 A CN 101579603A CN A200910087785X A CNA200910087785X A CN A200910087785XA CN 200910087785 A CN200910087785 A CN 200910087785A CN 101579603 A CN101579603 A CN 101579603A
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- sieve plate
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- hydrogen sulfide
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Abstract
The invention relates to a process for advanced treatment of waste alkali in hydrogen sulfide removal, belonging to the field of environmental protection in chemical industry. The process provided by the invention improves the effect of the oxidation reaction, improves the air lifting effect of the heavy hydrocarbons in the alkali and removes the stoppage phenomenon of the sieve shaped oxidation reactor. The process uses the deep liquid level reactor composed of a sieve plate and a down comer to oxidize the waste alkali of hydrogen sulfide removals, improves the gas-liquid mass transfer and reaction driving force through the reversed contacting of the gas-liquid, and obviously improves the oxidation effect of the alkali and the air lifting effect of the volatile organic materials; for waste alkali in hydrogen sulfide removal that the COD is 30,000 to 50,000 ppm, the deprivation rate is more than 98%. The specially designed down comer removes the collection of the solid suspension at the tray and overcomes the congestion phenomenon during the process. The process is suitable for advanced innocent treatment of waste alkali of pyrolysis gas in refinery, catalytic hydrogenation desulfurization tail gas and various sulfureted hydrogen containing tail gases after NaOH or Na2CO3 solution absorbes.
Description
Technical field
The present invention relates to a kind of new technology and oxidation reaction apparatus that is used for the waste alkali in hydrogen sulfide removal advanced treating.This technology can be used for hydrogen sulfide in oil plant and/or the natural gas after alkali lye absorb to be handled, and the efficient gas of the deep oxidation of inorganic sulphide and volatile organic matter is carried in the spent lye.Belong to the chemical industry environmental protection technical field.
Background technology
In oil plant cracking gas or vapour/diesel oil catalytic hydrogenation workshop section, can produce and contain certain density hydrogen sulfide (H in a large number
2S) tail gas, because the toxicity of hydrogen sulfide is bigger, can not be directly to airborne release.These tail gas adopt alkali lye (Na usually
2CO
3Or NaOH) absorbs processing, promptly hydrogen sulfide is converted into Na by the chemical absorbing mode
2S removes from tail gas.Contain a large amount of vulcanized sodium and a small amount of high-boiling hydrocarbon material in the spent lye that absorbs after handling, the COD of solution arrives up to ten million ppm up to hundreds of thousands.At present, enterprise adopts the high temperature air oxidation technology with Na more
2S is converted into Na
2SO
4Part hydrocarbons in the solution is discharged with tail gas, and the equipment that is adopted is sieve plate type/or packing type oxidation reactor, and heat medium is a steam, air/water steam and spent lye with and the stream mode at the bottom of tower, enter, the weary air of alkali lye after the oxidation and hydrocarbon-containifirst material is all discharged from cat head.This treatment technology has following shortcoming: (1) is because the superficial linear velocity in a column of liquid in reactor is very low, a spot of solid particle in the tower (being mainly the crystal of solid suspension and alkali lye) can not be taken out of from the top far away, thereby induce reaction device column plate sieve aperture and blender stop up, need regularly tear the tower deslagging open, influence ordinary production; (2) Na in the alkali lye
2The oxidation effectiveness of S is poor; (3) hot-air is carried weak effect to the gas of dissolving hydrocarbons in the spent lye, makes the COD concentration of processed alkali solution still more than 5000ppm, can't qualified discharge; (4) smell of the weary air of cat head is big, and there is the problem that exceeds standard and discharge in the concentration height of volatile organic matter.
At the problem that exists in the alkali liquor oxidized treatment process of present desulfurization, we have proposed a kind of new technology, can eliminate the problems referred to above fully, and promptly (1) eliminates the stifled tower phenomenon of oxidizing tower; (2) significantly improve Na
2The oxygenation efficiency of S, Na in the outlet spent lye
2The concentration of S can be controlled within the 10ppm; (3) significantly improve hot-air the gas of volatile organic matter in the spent lye is put forward effect, the COD of outlet alkali lye is between 500ppm-600ppm; (4) tail gas can qualified discharge through catalytic combustion.
Summary of the invention
In order to solve the technical problem in the existing waste lye oxidation technology, we have proposed following technology, and its flow process as shown in Figure 1.
Spent lye is extracted out with alkali pump from the salkali waste jar, earlier through the heat exchange of waste gas condensate cooler, by after the preheating of alkali lye preheater, with being steam heated to 110～130 ℃, enters the oxidation reactor top more again; Air is entered by the oxidation reactor bottom through being steam heated to 110～130 ℃.Gas-liquid counter-current flow and oxidation reaction takes place in oxidation reactor is with Na
2S is oxidized to Na
2SO
4, heavy hydrocarbon is discharged with cat head tail gas, to reduce the COD of outlet alkali lye, reaches discharge index.Outlet alkali lye enters the heat exchanger cooling, advances cooler cooling back discharging again.
For guaranteeing operating pressure in the tower, the oxidation reactor top is provided with pressure automatic regulating valve control exhaust emissions amount, and operating pressure is 0.5～0.6MPa in the reactor to keep.Tail gas is introduced into knockout drum, and (0.05～0.1MPa) sends to burning again to control blowdown presssure.
After adopting counter-current operation, automatic regulating valve tower level control at the bottom of the liquid storage amount employing tower in the oxidation reactor is to guarantee liquid residence time.
Oxidation reactor comprises polylith round sieve plate, it is characterized in that, a downspout all is installed on every block of round sieve plate, and downspout two ends discord round sieve plate contact, downspout is divided into the upper and lower after passing the round sieve plate, downspout top is provided with a hole at least at the height place of the above 2-6mm of round sieve plate, is used to prevent the accumulation of solid suspension on sieve plate.
This structural design has guaranteed the counter current contacting of gas-liquid two-phase, has increased the speed and the reaction motive force of gas/liquid mass transfer.Hot-air is up by the sieve plate hole, spent lye is descending by downspout, the perforate of solid suspension on the sieve plate on downspout and downspout flows into lower floor's column plate, thereby prevented the gathering of solid suspension at column plate, and a spot of solid suspension is discharged at the bottom of tower with alkali lye.The weary air that contains heavy hydrocarbon that this technology is come out can directly carry out harmless treatment by catalytic burning equipment.
Technology provided by the present invention is applicable to the harmless treatment of waste alkali in hydrogen sulfide removal, mild condition, and technology is simple, and easy operating has following beneficial effect: (1) eliminates the stifled tower phenomenon of waste lye oxidation tower, and (2) significantly improve Na
2The oxygenation efficiency of S, Na in the outlet spent lye
2The concentration of S can be controlled within the 10ppm, and (3) significantly improve hot-air the gas of volatile organic matter in the spent lye is put forward effect, and the COD of outlet alkali lye is within 500ppm, and (4) tail gas can qualified discharge through catalytic combustion.
The invention will be further described below in conjunction with the specific embodiment.
Description of drawings
The oxidation and the heavy hydrocarbon gas of Fig. 1 desulfurization spent lye are carried the process chart that removes
The structure of the dark liquid layer gas/liquid of Fig. 2 oxidation reactor and column plate inner member schematic diagram
The specific embodiment
The nucleus equipment of present technique is an oxidation reactor, and its structural representation is seen Fig. 2 (a), and the sieve tray structure is seen Fig. 2 (b), and downcomer structure is seen shown in Fig. 2 (c) and Fig. 2 (d).
Among the figure 1, the waste gas condensate cooler; 2, alkali lye preheater; 3, oxidation reactor; 4, knockout drum 5, sieve tray; 6, downspout.Dimensional units among Fig. 1 .2 is mm.
Reference examples:
Spent lye, air and water vapour be according to 2t/h, 180NM
3The flow proportional of/h (being converted under the standard state condition) and 200kg/h reaches about 110 ℃ the temperature of mixed liquor behind the static mixer mixed heat transfer, and the bottom from the oxidation reaction tower enters then.The oxidation reaction tower is sieve tray structure (a no downspout member), and air and liquid caustic soda all by sieve aperture and flow uply the air oxidation reaction of spent lye take place simultaneously, and the temperature of entire reaction tower is between 110-130 ℃.The spent lye of handling is discharged from cat head, enters heat exchanger spent lye is carried out preheating, and then enter heat exchanger and be cooled to room temperature, regulates the pH value and discharges after neutrality.The weary air that carries the 1100ppm-1500ppm heavy hydrocarbon is discharged from the cat head of oxidation reaction tower, directly emptying then.
In the experiment, COD content 35 in the pending spent lye, about 000ppm, Na wherein
2S contains 20, and about 000ppm, hydro carbons (mainly being heavy hydrocarbon) accounts for 15, about 000ppm.The time of staying of alkali lye in tower is 6 hours, in the oxidizing tower at the bottom of the tower and the temperature of cat head be respectively about 110 ℃ and 130 ℃, about 2 tons/hour of spent lye flow, air mass flow be 180 mark sides/hour.Through COD in the discharging salkali waste of above-mentioned PROCESS FOR TREATMENT 5,000-7, between the 000ppm, when the treating capacity of spent lye increased, waste liquid COD was higher.In addition, the obstruction of screen tray and blender at the bottom of the tower also often takes place in this reactor, influences ordinary production.
Embodiment 1
As shown in Figure 1, after static mixer mixes, be raised to 120 ℃ with steam (flow 160kg/h), enter dark liquid layer oxidation reactor from the top through the spent lye (flow is 2t/h) of alkali lye preheater 2 preheatings.Pressure 0.6MPa flow 300NM
3The air of/h is raised to 125 ℃ with the steam of flow 25kg/h after static mixer mixes, enter dark liquid layer oxidation reactor from the bottom.Spent lye oxidation reaction in oxidation reactor is discharged at the bottom of the oxidation reactor after (time of staying) 6 hours and is entered heat exchanger and reclaim heat, sample analysis and discharging after another heat exchanger drops to normal temperature again.
Oxidation reactor 3 is the sieve tray tower of band downspout 6.Air is up by sieve aperture, and suitable gas/liquid flow-rate ratio makes sieve tray 5 that the phenomenon of leakage not take place.Alkali lye flow to the lower screen orifice plate at gravity effect lower edge downspout from the upper sieve orifice plate, until discharging at the bottom of tower.Dark liquid layer between the column plate is the oxidation reaction zone of gas/liquid good mixing, be in the height agitated conditions, reaction effect is good, and solid suspension can not deposit at column plate, and a spot of solid suspension will enter lower floor's column plate from the perforate on the downspout top of downspout and next-door neighbour's sieve tray.The temperature of entire reaction tower is (between 120-135 ℃) relatively evenly.Because the adverse current gas of hot-air is proposed effect, make at the bottom of the tower that the content of heavy hydrocarbon greatly reduces than Comparative Examples in the alkali lye.Heavy hydrocarbon and other volatile organic matters of from the weary air that cat head is discharged, having high level, carrying the weary air of a certain amount of heavy hydrocarbon discharges from the cat head of oxidation reaction tower, recovery section higher boiling heavy hydrocarbon after waste gas condensate cooler 1 cooling carries out harmless treatment through the knockout drum 4 gas-liquid separations gas catalytic burning device that truncates then.
In the experiment, COD content 35 in the pending spent lye, about 000ppm, Na wherein
2S contains 20, and about 000ppm, hydro carbons (mainly being heavy hydrocarbon) accounts for 15, about 000ppm.The time of staying of alkali lye in tower is 6 hours, at the bottom of the oxidation reactor tower and the temperature of cat head be respectively about 125 ℃ and 120 ℃, the about 2t/h of spent lye flow, air mass flow is 180NM
3/ h.Through COD in the discharging salkali waste of above-mentioned PROCESS FOR TREATMENT is 500ppm, Na in the outlet spent lye
2The concentration of S is within 10ppm, and the obstruction of screen tray and blender at the bottom of the tower can not take place this reactor.
As shown in Figure 1, after static mixer mixes, be raised to 125 ℃ with steam (flow 250kg/h), enter dark liquid layer oxidation reactor from the top through the spent lye (flow is 3t/h) of heat exchanger preheating.Pressure 0.6MPa flow 400NM
3The air of/h is raised to 130 ℃ with the steam of flow 35kg/h after static mixer mixes, enter dark liquid layer oxidation reactor from the bottom.Spent lye oxidation reaction in oxidation reactor is discharged at the bottom of the oxidation reactor after (time of staying) 7 hours and is entered heat exchanger and reclaim heat, sample analysis and discharging after another heat exchanger drops to normal temperature again.
In the experiment, primary condition is 560ppm with embodiment 1 through COD in the discharging salkali waste of above-mentioned PROCESS FOR TREATMENT, Na in the outlet spent lye
2The concentration of S can be controlled within the 13ppm.
Claims (3)
1, a kind of technology that is used for the waste alkali in hydrogen sulfide removal advanced treating is characterized in that, may further comprise the steps:
The spent lye of Containing Sulfur sodium is heated to the top that enters oxidation reactor after 120 ℃ through steam; Pressure is that the air of 0.6MPa enters oxidation reactor from the bottom after steam is preheating to 125 ℃; Gas-liquid is counter current contacting in oxidation reactor, and the temperature in the tower is between 120-135 ℃; The time of staying 6-10 of spent lye in tower hour, at the bottom of tower, discharge spent lye, discharge weary air tail gas from cat head.
2, technology according to claim 1, it is characterized in that, oxidation reactor comprises polylith round sieve plate, a downspout all is installed on every block of round sieve plate, and downspout two ends discord round sieve plate contact, downspout is divided into the upper and lower after passing the round sieve plate, and downspout top is provided with a hole at least at the height place of the above 2-6mm of round sieve plate, is used to prevent the accumulation of solid suspension on sieve plate.
3, technology according to claim 1 is characterized in that, weary air tail gas carries out harmless treatment by catalytic combustion workshop section, realizes the qualified discharge of air.
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| CNA200910087785XA CN101579603A (en) | 2009-06-26 | 2009-06-26 | Process for advanced treatment of waste alkali in hydrogen sulfide removal |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104208992A (en) * | 2014-09-17 | 2014-12-17 | 宁波市化工研究设计院有限公司 | Method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur |
| CN104711023A (en) * | 2015-03-11 | 2015-06-17 | 郝天臻 | Treatment method for liquefied petroleum gas sweetening tail gas and alkaline residues and special equipment used in method |
| CN106396220A (en) * | 2015-07-28 | 2017-02-15 | 江苏吉华化工有限公司 | Chemical industry waste alkali liquid treatment method |
| CN108622968A (en) * | 2018-04-23 | 2018-10-09 | 上海理工大学 | The minimizing technology of Oil ＆ gas field in sulfur Hydrogen Sulfide in Sewage |
| CN112020392A (en) * | 2018-04-27 | 2020-12-01 | 林德有限责任公司 | Method for treating sulfide-containing spent lye |
| CN112041053A (en) * | 2018-04-27 | 2020-12-04 | 林德有限责任公司 | Method and apparatus for treating waste liquid |
-
2009
- 2009-06-26 CN CNA200910087785XA patent/CN101579603A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104208992A (en) * | 2014-09-17 | 2014-12-17 | 宁波市化工研究设计院有限公司 | Method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur |
| CN104208992B (en) * | 2014-09-17 | 2017-02-01 | 宁波市化工研究设计院有限公司 | Method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur |
| CN104711023A (en) * | 2015-03-11 | 2015-06-17 | 郝天臻 | Treatment method for liquefied petroleum gas sweetening tail gas and alkaline residues and special equipment used in method |
| CN104711023B (en) * | 2015-03-11 | 2016-07-27 | 河北精致科技有限公司 | Liquid gas sweetening tail gas and dreg control method and special equipment thereof |
| CN106396220A (en) * | 2015-07-28 | 2017-02-15 | 江苏吉华化工有限公司 | Chemical industry waste alkali liquid treatment method |
| CN108622968A (en) * | 2018-04-23 | 2018-10-09 | 上海理工大学 | The minimizing technology of Oil ＆ gas field in sulfur Hydrogen Sulfide in Sewage |
| CN112020392A (en) * | 2018-04-27 | 2020-12-01 | 林德有限责任公司 | Method for treating sulfide-containing spent lye |
| CN112041053A (en) * | 2018-04-27 | 2020-12-04 | 林德有限责任公司 | Method and apparatus for treating waste liquid |
| CN112041053B (en) * | 2018-04-27 | 2022-11-01 | 林德有限责任公司 | Method and apparatus for treating waste liquid |
| CN112020392B (en) * | 2018-04-27 | 2022-11-25 | 林德有限责任公司 | Method for treating sulfide-containing spent lye |
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Open date: 20091118 |