CN107213772A - The technique of zero discharge and system of a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas - Google Patents

The technique of zero discharge and system of a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas Download PDF

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CN107213772A
CN107213772A CN201710649821.1A CN201710649821A CN107213772A CN 107213772 A CN107213772 A CN 107213772A CN 201710649821 A CN201710649821 A CN 201710649821A CN 107213772 A CN107213772 A CN 107213772A
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oxygen
sulfur dioxide
solution
tail gas
ammonia
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CN107213772B (en
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薛斌
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Dalian Branch Engineering Technology Co Ltd
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Dalian Branch Engineering Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/58—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8634—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/90—Injecting reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia

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  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The present invention provides the technique of zero discharge and system of a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas, comprises the following steps：Reacted using solution with the oxygen and sulfur dioxide in tail gas, the oxygen and sulfur dioxide in tail gas are reduced to 0~2vol% and 0~30ppm respectively, can all simultaneously (mixed) enters in coal gas；Described oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas are：Ammonia is produced during removing wherein hydrogen sulfide and hydrogen cyanide as alkali source using in coal gas solid salt or waste liquid and/or sulphur, burn the oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas produced respectively when extracting sulfuric acid or sulphur ammonium.The technique and system make oxygen and content of sulfur dioxide after reaction in tail gas be reduced to 0~2vol% and 0~30ppm respectively, thoroughly solve the discharge of tail gas.

Description

A kind of zero-emission work of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas Skill and system
Technical field
The present invention relates to tail gas disposal technique, more particularly to a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia The technique of zero discharge and system of tail gas.
Background technology
At present to using in coal gas ammonia be that alkali source removes the solid salt wherein produced during hydrogen sulfide and hydrogen cyanide or given up Liquid and/or sulphur processing, there is two methods of burning extracting sulfuric acid or sulphur ammonium.Both approaches are first solid salt or waste liquid And/or sulphur is burned as the process gas containing sulfur dioxide, sulfuric acid process absorbs production sulfuric acid by converting, finally needed tail The environmental protection standard that sulfur dioxide treatment in gas is directly discharged to satisfaction；Sulphur ammonium method uses the dioxy in ammonia absorption process gas Change sulphur production sulphur ammonium, be finally also required to the environmental protection standard that the ammonia and sulfur dioxide treatment in tail gas are directly discharged to satisfaction.
Raising and increasingly strict, the skill of control sulfur dioxide in tail gas or sulfur dioxide and ammonia content with environmental protection standard The increase of art difficulty.
Therefore, in the urgent need to developing a kind of new tail gas treatment process and system.
The content of the invention
It is an object of the present invention to it is big for current sulfur dioxide in tail gas or sulfur dioxide and ammonia treatment technical difficulty, Propose the technique of zero discharge and system of a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas, the system and system Thoroughly solve the discharge of tail gas.
To achieve the above object, the technical solution adopted by the present invention is：A kind of oxygen-containing and sulfur dioxide or oxygen-containing and dioxy Change the technique of zero discharge of sulphur and ammonia tail gas, comprise the following steps：Using solution and oxygen-containing and sulfur dioxide or oxygen-containing and titanium dioxide The tail gas of sulphur and ammonia is reacted, and the oxygen and sulfur dioxide in tail gas are reduced to 0~2vol% and 0~30ppm respectively, make it Can all simultaneously (mixed) enters in coal gas, so as to realize zero-emission；Described oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia Tail gas source is：Ammonia is produced during removing wherein hydrogen sulfide and hydrogen cyanide as alkali source using in coal gas solid salt or waste liquid And/or sulphur, burn the oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail produced respectively when extracting sulfuric acid or sulphur ammonium Gas；
The solution ph 8~11, including following each component：
0~3g/l suspensions sulphur, 0~10g/l ammonia, 0~6g/l NH4HS, 0~4g/l (NH4)2S, 0~3g/l NH4CNS、0 ~2g/l NH4CN, 0~300g/l (NH4) SCN, 0~300g/l (NH4)2S2O3, 0~12g/l (NH4)2Sx, 0~20g/l (NH4)2SO4, 0~16g/l NH4HCO3, 0~10g/l (NH4)2CO3And water.
The content of described oxygen-containing and SO 2 tail gas, wherein oxygen and sulfur dioxide is as follows：
0.1~100g/m3Oxygen, 50~2000mg/m3Sulfur dioxide.
Described oxygen-containing and sulfur dioxide and ammonia tail gas, the content of wherein oxygen and sulfur dioxide and ammonia are as follows：
0.1~110g/m3Oxygen, 50~2000mg/m3Sulfur dioxide, 30~3000mg/m3Ammonia.
Further, 0.01~1wt% catalyst is also included in the solution, the catalyst is：Picric acid (PIA) or HPF (Kun, cobalt, Fe compound type), PDS (ichthyodin of main component binuclear phthalocyanine cobalt sulfone ten) or tannin extract (main component is tannin) or PDS+ tannin extracts.
Explanation：HPF and PDS main components refer to the professional book of Zhongye Coke Resistance Engineering Technology Co., Ltd's publication《It is modern Coking production technical manual》Save the application of the desulfurization of 8.5.1HPF methods and the section other desulphurization catalysts of 8.5.2.6 on ADA devices.
NH in oxygen and solution in tail gas4HS、(NH4)2S、NH4CNS、(NH4)2S2O3、(NH4)2SxReaction, makes tail after reaction Oxygen content in gas is reduced to 0~2vol%.Sulfur dioxide in tail gas and NH in solution4HS、(NH4)2S reacts, and makes tail after reaction Content of sulfur dioxide in gas is reduced to 0~30ppm.Oxygen and sulfur dioxide are reduced to 0~2vol% and 0~30ppm, energy respectively Enough all simultaneously (mixed) enters in coal gas, so as to realize zero-emission.
Another object of the present invention also discloses a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas Zero discharging system, including reaction tower includes one or more absorber portions in the reaction tower, and the multiple absorber portion is from lower On be arranged in series；Make-up solution entrance and offgas outlet are provided with the top of the reaction tower, the reaction tower bottom, which is provided with, to be followed Ring liquid is exported and oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia gas inlet, the circulation fluid outlet respectively with solution Entrance is connected with solution line is sent outside.The operation principle of the reaction tower：Oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and Ammonia tail gas flows through reaction tower from bottom to up, with top-down solution counter current contacting.In the epimere make-up solution of reaction tower. The hypomere of reaction tower also sends part solution outside, to keep the material balance of system in addition to circulation.Make-up solution and send solution outside Measure as the 1~60% of circulating fluid flow rate.
When including multiple absorber portions in the reaction tower, each absorber portion reaction can be by the way of solution circulation.It is described anti- When answering in tower including single absorber portion, make-up solution is directly mixed into reaction tower with circulation solution.
Further, when the reaction tower includes an absorber portion, the absorber portion is empty spray section, packing section or board-like Section.
Further, when the reaction tower includes multiple absorber portions, absorber portion is empty spray section, packing section or board-like section of one kind Or it is a variety of.
Another object of the present invention also discloses a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas Zero discharging system, including one-level Venturi tube, primary liquor groove and circulating pump, the one-level Venturi tube is located at primary liquor The top of groove, the pump entry and primary liquor trench bottom circulation solution outlet, the circulating-pump outlet respectively with Make-up solution pipeline, send solution line outside and connected with the entrance of one-level Venturi tube；Tail is provided with the top of the primary liquor groove Gas is exported；The trunnion of the one-level Venturi tube is oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia gas inlet, institute The entrance for stating one-level Venturi tube is solution inlet.
When the Zero discharging system of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas only includes one-level venturi Guan Shi, make-up solution is directly mixed into one-level Venturi tube with circulation solution.Make-up solution is circulation with the amount of solution is sent outside The 1~60% of amount.
Another object of the present invention also discloses a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas Zero discharging system, including Venturi tube and solution tank include one-level Venturi tube, primary liquor groove, two grades of Venturi tubes, two Level solution tank and circulating pump；
Two grades of Venturi tubes are located at the top of two grades of solution tanks, and the pump entry is followed with two grades of solution trench bottoms Ring taphole is connected, and is additionally provided with the second offgas outlet at the top of two grades of solution tanks, the circulating-pump outlet respectively with outside Send the entrance connection of solution line and two grades of Venturi tubes；The trunnion of two grades of Venturi tubes is that the second gas inlet is (oxygen-containing With sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia gas inlet)；
The one-level Venturi tube is located at the top of primary liquor groove, primary liquor trench bottom circulation solution outlet with The first offgas outlet is additionally provided with the top of the second replenisher entrance connection of two grades of solution groove sidewalls, the primary liquor groove；Institute The trunnion for stating one-level Venturi tube is the first gas inlet, and first gas inlet is connected with the second offgas outlet, described one The entrance of level Venturi tube is the first make-up solution entrance.
When the Zero discharging system of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas includes one-level Venturi tube During with two grades of Venturi tubes, one-level Venturi tube uses make-up solution, and two grades of Venturi tubes use circulation solution.
The present invention a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas technique of zero discharge and system are fitted For to using in coal gas ammonia remove the solid salt or waste liquid and/or sulphur that wherein produce during hydrogen sulfide and hydrogen cyanide as alkali source Sulphur, burns the place of the oxygen-containing and sulfur dioxide produced respectively when extracting sulfuric acid or sulphur ammonium or oxygen-containing and sulfur dioxide and ammonia tail gas Reason, compared with prior art with advantages below：
1) solution that uses of the present invention can react with the oxygen in tail gas and sulfur dioxide, make oxygen after reaction in tail gas and Content of sulfur dioxide is reduced to 0~2vol% and 0~30ppm respectively.
2) after managing tail gas can all simultaneously (mixed) enters in coal gas, it is of the invention in tail gas so as to realize tail gas zero-emission Oxygen and sulfur dioxide handled, tail gas is mixed into safe range of the Control for Oxygen Content after coal gas below LEL It is interior, tail gas is mixed into the control of the content of sulfur dioxide after coal gas and do not blocked up in the trace sulphur that sulfur dioxide reacts generation with hydrogen sulfide In the range of plug follow-up equipment and pipeline.
Brief description of the drawings
Fig. 1 is the structure of the Zero discharging system of oxygen-containing embodiment 1 and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas Schematic diagram；
Fig. 2 is the structure of the Zero discharging system of oxygen-containing embodiment 2 and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas Schematic diagram；
Fig. 3 is the structure of the Zero discharging system of oxygen-containing embodiment 3 and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas Schematic diagram.
Wherein reference is respectively：
1- one-level Venturi tubes；2- primary liquor grooves；Bis- grades of Venturi tubes of 3-；Bis- grades of solution tanks of 4-；5- circulating pumps；6- is anti- Answer tower；7- sky spray sections；8- packing sections；9- column plate sections.
Embodiment
The present invention is further described with reference to embodiments：
Embodiment 1
Present embodiment discloses a kind of oxygen-containing and sulfur dioxide or the Zero discharging system of oxygen-containing and sulfur dioxide and ammonia tail gas, Its structure is as shown in Figure 1：Including one-level Venturi tube 1, primary liquor groove 2 and circulating pump 5, the one-level Venturi tube 1 is located at The top of primary liquor groove 2, the entrance of circulating pump 5 is connected with the bottom cycle taphole of primary liquor groove 2, the circulating pump 5 outlets are connected with make-up solution pipeline, the entrance for sending solution line and one-level Venturi tube 1 outside respectively；The primary liquor groove 2 Top is provided with offgas outlet；The trunnion of the one-level Venturi tube 1 is oxygen-containing and sulfur dioxide and ammonia gas inlet, described one The entrance of level Venturi tube 1 is solution inlet.
The technique of zero discharge of oxygen-containing and sulfur dioxide and ammonia tail gas is completed using said system, is comprised the following steps：
It is described to contain 3g/m3Oxygen and 500mg/m3Sulfur dioxide and 150mg/m3Ammonia enters the trunnion of one-level Venturi tube 1, institute State containing 1~2g/l suspensions sulphur, 2~5g/l ammonia, 2~3g/l NH4HS, 1~2g/l (NH4)2S, 1~2g/l NH4CNS, 1~ 2g/l NH4CN, 150~240g/l (NH4) SCN, 100~160g/l (NH4)2S2O3, 3~5g/l (NH4)2Sx, 2~6g/l (NH4)2SO4, 3~6g/l NH4HCO3, 1~2g/l (NH4)2CO3, water and 0.3~0.5wt% catalyst solution from one-level text The entrance of venturi 1 enters, and the tail gas and solution after close contact, enter in one-level Venturi tube 1 from one-level Venturi tube 1 Enter solution tank 2.
In one-level Venturi tube 1, oxygen and NH in solution in the tail gas4HS、(NH4)2S、NH4CNS、(NH4)2S2O3、 (NH4)2SxReaction, sulfur dioxide and NH4HS、(NH4)2S reacts, and oxygen and content of sulfur dioxide in the tail gas is reduced respectively To 0~2vol% and 0~30ppm.
Tail gas is separated with solution in solution tank 2 after reaction, and tail gas is discharged by the top of solution tank 2 after reaction, all simultaneously (mixed) enters in coal gas.
Solution falls into the bottom of solution tank 2, is extracted out by circulating pump 5, and 80~85% are recycled into the entrance of one-level Venturi tube 1, 15~20% outer rows.Enter the entrance of one-level Venturi tube 1 with the make-up solution of outer row's solution even.
Embodiment 2
Present embodiment discloses a kind of oxygen-containing and sulfur dioxide or the Zero discharging system of oxygen-containing and sulfur dioxide and ammonia tail gas, Its structure is as shown in Figure 2：Including one-level Venturi tube 1, primary liquor groove 2, two grades of Venturi tubes 3, two grades of solution tanks 4 and circulation Pump 5.Two grades of Venturi tubes 3 are located at the top of two grades of solution tanks 4, and the entrance of circulating pump 5 is followed with two grades of bottoms of solution tank 4 Ring taphole is connected, and the top of two grades of solution tanks 4 is additionally provided with the second offgas outlet, the circulating pump 5 export respectively with The entrance that solution conduit is sent outside with two grades of Venturi tubes 3 is connected；The trunnion of two grades of Venturi tubes 3 is the second (oxygen-containing and dioxy Change sulphur) gas inlet.
The one-level Venturi tube 1 is located at the top of primary liquor groove 2, and the bottom cycle solution of primary liquor groove 2 goes out Mouth is connected with the second replenisher entrance of two grades of side walls of solution tank 4, and the top of primary liquor groove 2 is additionally provided with the first tail gas and gone out Mouthful；The trunnion of the one-level Venturi tube 1 is the first gas inlet, and first gas inlet is connected with the second offgas outlet, The entrance of the one-level Venturi tube 1 is the first make-up solution entrance.
The technique of zero discharge of oxygen-containing and SO 2 tail gas is completed using said system, is comprised the following steps：
It is described to contain 4g/m3Oxygen and 400mg/m3Sulfur dioxide enters the trunnion of two grades of Venturi tubes 3, described to contain 1~3g/l Suspension sulphur, 3~8g/l ammonia, 4~5g/l NH4HS, 3~4g/l (NH4)2S, 1~3g/l NH4CNS, 0.5~2g/l NH4CN、 120~260g/l (NH4) SCN, 110~1500g/l (NH4)2S2O3, 4~6g/l (NH4)2Sx, 3~10g/l (NH4)2SO4, 4~ 7g/l NH4HCO3, 2~3g/l (NH4)2CO3, water and 0.4~0.6wt% catalyst solutions enter from two grades of Venturi tubes 3 Mouth enters, and the tail gas and solution after close contact, enter two grades of solution in two grades of Venturi tubes 3 from two grades of Venturi tubes 3 Groove 4.
In two grades of Venturi tubes 3, oxygen and NH in solution in the tail gas4HS、(NH4)2S、NH4CNS、(NH4)2S2O3、 (NH4)2SxReaction, sulfur dioxide and NH4HS、(NH4)2S reacts.
Tail gas is separated with solution in two grades of solution tanks 4 after reaction, and tail gas is discharged by two grades of tops of solution tank 4 after reaction, Into the trunnion of one-level Venturi tube 1.
Solution falls into two grades of bottoms of solution tank 4, is extracted out by circulating pump 5, and 80~94%, which are recycled into two grades of Venturi tubes 3, enters Mouthful, 6~20% outer rows.
Enter the entrance of one-level Venturi tube 1 with the make-up solution of outer row's solution even, with carrying out two grades of tail gas of solution tank 4 one In level Venturi tube 1 after close contact, enter primary liquor groove 2 from one-level Venturi tube 1.
In one-level Venturi tube 1, oxygen and NH in solution in tail gas4HS、(NH4)2S、NH4CNS、(NH4)2S2O3、(NH4)2SxReaction, sulfur dioxide and NH4HS、(NH4)2S reacts, make oxygen and content of sulfur dioxide in the tail gas be reduced to 0 respectively~ 2vol% and 0~30ppm.
Tail gas is separated with solution in primary liquor groove 2 after reaction, and tail gas is discharged by the top of primary liquor groove 2 after reaction, All simultaneously (mixed) enters in coal gas.
Solution falls into the bottom of primary liquor groove 2, enters two grades of bottoms of solution tank 4 by fluid-tight.
Embodiment 3
Present embodiment discloses a kind of oxygen-containing and sulfur dioxide or the Zero discharging system of oxygen-containing and sulfur dioxide and ammonia tail gas, Its structure is as shown in Figure 3：Including reaction tower 6, empty spray section 7, packing section 8 and column plate section 9.The empty spray section 7, packing section 8 and tower Plate section 9 is arranged in series from bottom to top.The top of reaction tower 6 is provided with make-up solution entrance and offgas outlet, the reaction tower Bottom is provided with circulation fluid outlet and oxygen-containing and sulfur dioxide and ammonia gas inlet, the circulation fluid outlet respectively with solution inlet Connected with solution line is sent outside.
The technique of zero discharge of oxygen-containing and sulfur dioxide and ammonia tail gas is completed using said system, is comprised the following steps：
It is described to contain 12g/m3Oxygen and 200mg/m3Sulfur dioxide and 800mg/m3Ammonia tail gas enters reaction tower 6 from bottom to up, It is described to contain 1~2g/l suspensions sulphur, 6~8g/l ammonia, 5~6g/l NH4HS, 3~4g/l (NH4)2S, 2~3g/l NH4CNS、1 ~2g/l NH4CN, 160~21g/l (NH4) SCN, 180~220g/l (NH4)2S2O3, 6~9g/l (NH4)2Sx, 3~6g/l (NH4)2SO4, 3~7g/l NH4HCO3, 5~6g/l (NH4)2CO3, water and 0.2~0.4wt% catalyst make-up solution from The top of reaction tower 6 enters, and the tail gas and solution are in reaction tower 6 after close contact, and tail gas is arranged by the top of reaction tower 6 after reaction Go out, all simultaneously (mixed) enters in coal gas.
In reaction tower 6, oxygen and NH in solution in the tail gas4HS、(NH4)2S、NH4CNS、(NH4)2S2O3、(NH4)2Sx Reaction, sulfur dioxide and NH4HS、(NH4)2S reacts, make oxygen and content of sulfur dioxide in the tail gas be reduced to 0 respectively~ 2vol% and 0~30ppm.
Enter the top of reaction tower 6 with the make-up solution of outer row's solution even, with falling into packing section after tail gas counter current contacting.
The solution of the bottom of reaction tower 6, is extracted out by circulating pump 5, and 50~60%, which are recycled into the hypomere of reaction tower 6 sky spray section, enters Mouthful, 25~35% are recycled into the stage casing packing section entrance of reaction tower 6,10~20% outer rows.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology The scope of scheme.

Claims (7)

1. the technique of zero discharge of a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas, it is characterised in that including Following steps：Reacted, respectively the oxygen in tail gas and sulfur dioxide are dropped with the oxygen and sulfur dioxide in tail gas using solution As little as 0~2vol% and 0~30ppm, can be fully incorporated in coal gas；Described oxygen-containing and sulfur dioxide or oxygen-containing and dioxy Change sulphur and ammonia tail gas is：The solid salt or useless that ammonia is produced during removing wherein hydrogen sulfide and hydrogen cyanide as alkali source using in coal gas Liquid and/or sulphur, burn the oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia produced respectively when extracting sulfuric acid or sulphur ammonium Tail gas；
The solution ph 8~11, including following each component：
0~3g/l suspensions sulphur, 0~10g/l ammonia, 0~6g/l NH4HS, 0~4g/l (NH4)2S, 0~3g/l NH4CNS, 0~2g/ l NH4CN, 0~300g/l (NH4) SCN, 0~300g/l (NH4)2S2O3, 0~12g/l (NH4)2Sx, 0~20g/l (NH4)2SO4、 0~16g/l NH4HCO3, 0~10g/l (NH4)2CO3And water.
2. the technique of zero discharge of oxygen-containing according to claim 1 and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas, its It is characterised by, 0.01~1wt% catalyst is also included in the solution, and the catalyst is：Picric acid PIA or HPF, PDS or Tannin extract or PDS+ tannin extracts.
3. the Zero discharging system of a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas, it is characterised in that including Include one or more absorber portions in reaction tower, the reaction tower, the multiple absorber portion is arranged in series from bottom to top；It is described anti- Top of tower is answered to be provided with make-up solution entrance and offgas outlet, the reaction tower bottom is provided with circulation fluid outlet and oxygen-containing and two Sulfur oxide or oxygen-containing and sulfur dioxide and ammonia gas inlet, the circulation fluid outlet is respectively with solution inlet and sending solution line outside Connection.
4. the Zero discharging system of oxygen-containing according to claim 3 and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas, its It is characterised by, when the reaction tower includes an absorber portion, the absorber portion is empty spray section, packing section or board-like section.
5. the Zero discharging system of oxygen-containing according to claim 3 and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas, its It is characterised by, when the reaction tower includes multiple absorber portions, absorber portion is empty spray section, packing section or board-like section of one or more.
6. the Zero discharging system of a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas, it is characterised in that including One-level Venturi tube, primary liquor groove and circulating pump, the one-level Venturi tube are located at the top of primary liquor groove, the circulation Pump intake and primary liquor trench bottom circulation solution outlet, the circulating-pump outlet respectively with make-up solution pipeline, send outside Solution line is connected with the entrance of one-level Venturi tube；Offgas outlet is provided with the top of the primary liquor groove；The one-level text The trunnion of venturi is oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia gas inlet, and the one-level Venturi tube enters Mouth is solution inlet.
7. the Zero discharging system of a kind of oxygen-containing and sulfur dioxide or oxygen-containing and sulfur dioxide and ammonia tail gas, it is characterised in that including Venturi tube and solution tank include one-level Venturi tube, primary liquor groove, two grades of Venturi tubes, two grades of solution tanks and circulating pump；
Two grades of Venturi tubes are located at the top of two grades of solution tanks, and the pump entry and two grades of solution tank bottom cycles are molten Be additionally provided with the second offgas outlet at the top of liquid outlet, two grades of solution tanks, the circulating-pump outlet respectively with send outside it is molten The entrance connection of liquid pipeline and two grades of Venturi tubes；The trunnion of two grades of Venturi tubes is the second gas inlet；
The one-level Venturi tube is located at the top of primary liquor groove, and the primary liquor trench bottom circulation solution is exported and two grades The first offgas outlet is additionally provided with the top of the second replenisher entrance connection of solution groove sidewall, the primary liquor groove；Described one The trunnion of level Venturi tube is the first gas inlet, and first gas inlet is connected with the second offgas outlet, the one-level text The entrance of venturi is the first make-up solution entrance.
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CN201832555U (en) * 2010-11-05 2011-05-18 中国石油化工股份有限公司 Optimized two-circulating flue gas dust removal and desulfurization device
CN102580475A (en) * 2012-02-17 2012-07-18 宣化钢铁集团有限责任公司 Method for recycling sulfuric acid tail gas in gas purification AS desulfurization process
CN104338428A (en) * 2014-10-24 2015-02-11 无锡伊佩克科技有限公司 Compound absorbent used for waste gas treatment and treatment method
CN105084326A (en) * 2014-05-09 2015-11-25 托普索公司 Production of sulfuric acid from coke oven gas desulfurization product
CN105600990A (en) * 2016-01-19 2016-05-25 天津市碳一有机合成工程设计有限公司 Method for recycling coke oven gas desulfurization and decyanation waste liquid to reclaim sulfur, ammonium sulfate and catalysts

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201832555U (en) * 2010-11-05 2011-05-18 中国石油化工股份有限公司 Optimized two-circulating flue gas dust removal and desulfurization device
CN102580475A (en) * 2012-02-17 2012-07-18 宣化钢铁集团有限责任公司 Method for recycling sulfuric acid tail gas in gas purification AS desulfurization process
CN105084326A (en) * 2014-05-09 2015-11-25 托普索公司 Production of sulfuric acid from coke oven gas desulfurization product
CN104338428A (en) * 2014-10-24 2015-02-11 无锡伊佩克科技有限公司 Compound absorbent used for waste gas treatment and treatment method
CN105600990A (en) * 2016-01-19 2016-05-25 天津市碳一有机合成工程设计有限公司 Method for recycling coke oven gas desulfurization and decyanation waste liquid to reclaim sulfur, ammonium sulfate and catalysts

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