CN106744722B - A kind of regeneration technology of acetylene cleaning Waste Sulfuric Acid - Google Patents
A kind of regeneration technology of acetylene cleaning Waste Sulfuric Acid Download PDFInfo
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- CN106744722B CN106744722B CN201611226230.5A CN201611226230A CN106744722B CN 106744722 B CN106744722 B CN 106744722B CN 201611226230 A CN201611226230 A CN 201611226230A CN 106744722 B CN106744722 B CN 106744722B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a kind of regeneration technologies of acetylene cleaning Waste Sulfuric Acid.Using acetylene cleaning Waste Sulfuric Acid as raw material, burnt in pyrolysis furnace heat needed for providing cracking reaction by fuel, make acetylene cleaning Waste Sulfuric Acid that cracking reaction occur under pyrolysis furnace high temperature, it ultimately generates containing sulfur dioxide, sulfur trioxide, oxygen, phosphorus pentoxide, carbon dioxide, water vapour, nitrogen, the high-temperature flue gas of flue dust etc., high-temperature flue gas is cooling through furnace gas, air preheat, close acid-scrubbing cleaning, it is dry, it converts twice, qualified finished product sulfuric acid is produced after the processes such as absorption twice, then acetylene cleaning device is returned to reuse, tail gas discharges after spray-absorption and electric demisting.The present invention solves the problems, such as that acetylene cleaning Waste Sulfuric Acid is reluctant, realizes recycling for Sulphur ressource, and the rate of recovery of Waste Sulfuric Acid can achieve 98% or more.
Description
Technical field
The invention belongs to technical field of environmental protection in chemical industry, and in particular to a kind of regeneration technology of acetylene cleaning Waste Sulfuric Acid.
Background technique
Due to containing impurity in calcium carbide, in the thick acetylene gas that calcium carbide wet process acetylene technique generates containing more water and
Sulphur, phosphorus etc. if bringing downstream unit into will lead to equipment corrosion and catalyst poisoning, and influence the quality of downstream product.At present
The most commonly used is 98% concentrated sulfuric acids for acetylene cleaning process, remove the vulcanization in thick acetylene gas using its strong oxidizing property and dehydration property
Hydrogen, hydrogen phosphide and water.But the concentrated sulfuric acid for a long time be recycled after, concentration constantly reduces, the impurity such as organic matter and sulphur, phosphorus by
Cumulative more, sulfuric acid concentration just cannot be used continuously when being down to 75% or less, be discharged as the three wastes.
The treatment process of acetylene cleaning Waste Sulfuric Acid is mainly include the following types: 1. neutralisations at present, acetylene cleaning Waste Sulfuric Acid with
Producing cement clinker after carbide slag will neutralize, this technique are unfavorable for recycling for Sulphur ressource, meanwhile, excessive sulfate can be serious
Cement Quality is influenced, so additive amount has stringent limitation in cement, in addition neutralizes, many waste water can be generated after filters pressing, generate
Secondary pollution.2. decomposing phosphate rock phosphate fertilizer made of stones brings meeting in phosphate fertilizer into due to containing more organic matter in acetylene cleaning Waste Sulfuric Acid
Generate secondary pollution.3. aoxidizing concentration technology, the method which first passes through catalysis oxidation removes the organic matter in Waste Sulfuric Acid, so
Vacuum concentration concentrate is being carried out afterwards, which is not thorough the organic matter processing in spent acid, and organic substance residues are high, while can not remove
The a large amount of inorganic matters contained in spent acid are removed, the concentration after vacuum concentration is low, can only be to 95%, to equipment choice requirement height, Wu Falian
Continuous stable operation.
For existing acetylene cleaning sulfur waste acid treatment process all in the presence of that can not operate continuously, waste acid treatment amount is small, handles not thorough
The problems such as bottom, secondary pollution, the wasting of resources, the feature of environmental protection and economy are poor, bring to calcium carbide acetylene production enterprise very big
Environmental protection and economic pressures.
Summary of the invention
The present invention be directed to above-mentioned statuses, and a kind of regeneration technology of the acetylene cleaning Waste Sulfuric Acid proposed, are particularly suitable for
The Waste Sulfuric Acid containing impurity such as more organic matter, water and phosphoric acid that acetylene cleaning device generates.
Maximum feature of the invention is that waste acid treatment amount is big, and operating flexibility is big；Continuous operation, safety and stability；Processing
Thoroughly, superior product quality, exhaust gas discharge are far below national standard；Low energy consumption, and fuel source is extensive, and operating cost is low；Sulphur returns
High income can achieve 98% or more.
The present invention is implemented as follows: the regeneration technology of acetylene cleaning Waste Sulfuric Acid, it is characterised in that: with acetylene cleaning sulfur waste
Acid makees raw material, and fuel and oxygen-containing gas are sprayed into pyrolysis furnace by burner and burnt, heat needed for providing cracking reaction
Amount after reaching reaction temperature, sprays into pyrolysis furnace after acetylene cleaning Waste Sulfuric Acid is atomized by spent acid spray gun and carries out cracking reaction, make second
Alkynes Waste Sulfuric Acid is generated in pyrolysis furnace containing sulfur dioxide, sulfur trioxide, oxygen, phosphorus pentoxide, carbon dioxide, water vapour, nitrogen
The high-temperature flue gas of gas, flue dust, high-temperature flue gas through furnace gas cooling, air preheat, closing acid-scrubbing cleaning, drying, twice conversion, twice
Qualified finished product sulfuric acid is produced after absorbing process, relieving haperacidity tail gas after spray-absorption and electric demisting by discharging.
Generally, the primary raw material of acetylene cleaning waste Acid Recovery Process of the present invention is containing sulfuric acid, water, organic matter, phosphorus
The acetylene cleaning Waste Sulfuric Acids of acid, inorganic salts, sulfuric acid content >=70% in acetylene cleaning Waste Sulfuric Acid；The fuel includes: natural
It is air-liquid liquefied oil gas, sulphur, sour gas, dry gas, hydrogenolysis gassing, light oil, one or more of in mink cell focus；It is described oxygenous
Body be air, oxygen-enriched air or other contain the gas of oxygen, the charging temperature of oxygen-containing gas is room temperature or more.
The spent acid cracking reaction temperature is >=800 DEG C；Oxygen mole concentration in pyrolysis furnace exiting flue gas is 0 ~ 10%；
Sulfur dioxide molar concentration >=4%.
The high-temperature flue gas of the cracking outlet of still cools down the equipment used firstly the need of cooling down >=700 DEG C
For burner-gas cooler.
The burner-gas cooler includes heat-dissipating pipe and ash bucket；The material of burner-gas cooler is high-alloy steel resistant to high temperature or carbon
SiClx.
The high-temperature flue gas come out from burner-gas cooler enters the hot-air that air preheater and hot-air blower are sent
It exchanges heat, enters efficiently humidification washer progress acid-scrubbing cleaning after recycling thermal energy；Into hot-air one of air preheater
Divide the normal temperature air sucked from atmosphere from cold air blower, another part is empty from the high temperature that air preheater outlet returns
Gas is sent into air preheater by hot-air blower after the two mixing；High temperature air a part of air preheater outlet returns
To hot-air blower, a part enters pyrolysis furnace as combustion air.
Flue-gas temperature >=400 DEG C of the air preheater outlet；Air themperature >=300 DEG C of air preheater import.
The high-temperature flue gas come out from air preheater initially enters efficiently humidification washer and carries out adiabatic humidification cooling
And clean, further cool down dedusting and NOx subsequently into filling cooling tower, and purified electricity removes the flue gas of filling cooling tower again out
Day with fog goes drying tower to be dried after removing acid mist.
The relieving haperacidity tail gas of second absorption tower outlet is inhaled remaining two in tower absorbing liquid spray-absorption tail gas through tail first
Then sulfur oxide is inhaled after electrostatic precipitator removes acid mist through two-stage tail and is discharged, exhaust emissions concentration reaches SO2≤50mg/m3, Nox≤
50mg/m3, acid mist≤5mg/m3。
The absorbing liquid uses alkaline aqueous solution or hydrogen peroxide.
Present invention process solves the problems, such as that acetylene cleaning Waste Sulfuric Acid is reluctant, realizes recycling for Sulphur ressource,
The rate of recovery of this technique Waste Sulfuric Acid can achieve 98% or more.
Detailed description of the invention
Fig. 1 is the flow diagram for illustrating acetylene cleaning waste Acid Recovery Process of the embodiment of the present invention.
Fig. 1 is to be used to provide further understanding of the present invention, and constitute part of specification, and following specific
Embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In figure, 1- spent acid pump；2- spent acid spray gun；3- burner；4- pyrolysis furnace；5- furnace gas cold air device；6- air preheater；
7- cold air blower；8- hot-air blower；The efficient humidifier of 9-；10- packed tower；11- purifies electrostatic precipitator；12- tail is inhaled electricity and is removed
Day with fog；13- drying tower；The first absorption tower 14-；15- second absorption tower；16- drying tower circulating slot；17- mono- inhales tower circulating slot；
18- bis- inhales tower circulating slot；19- finished acid underground tank；20- finished acid tank；21- lye tank (vat)；22- tail inhales circulating pump；23- tail is inhaled
Tower；24- main blower；The IIIth heat exchanger of 25-；The Ith heat exchanger of 26-；Mono- section of electric furnace of 27-；28- converter；29- the Vth exchanges heat
Device；The IVth heat exchanger of 30-；The IIth heat exchanger of 31-；Tetra- sections of electric furnaces of 32-.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
The technical process of following embodiment is referring to attached drawing 1.
Embodiment 1
1. Pintsch process
Combustion in pyrolysis furnace (4) is sprayed into after being first sufficiently mixed natural gas and 500 DEG C of hot-air in burner (3)
It burns, maintains furnace temperature at 1000 DEG C.Then acetylene cleaning Waste Sulfuric Acid is boosted into 0.3MPa by spent acid pump (1), with compressed air
Progress Pintsch process reaction in pyrolysis furnace is sprayed into after being passed through spent acid spray gun (2) atomization together, is ultimately generated containing sulfur dioxide, three oxygen
Change the high-temperature flue gas of sulphur, phosphorus pentoxide, carbon dioxide, water, nitrogen, flue dust etc..
2. furnace gas is cooling
High-temperature flue gas comes out from pyrolysis furnace (4) and initially enters natural cooling in burner-gas cooler (5), tentatively cools to 700
DEG C or more after enter air preheater (6), the flue dust to settle down and molten state salt are discharged by burner-gas cooler ash bucket.
3. air preheat
High-temperature flue gas from burner-gas cooler (5) enters 500 that air preheater (6) and hot-air blower (8) are sent
DEG C hot-air heat exchange, recovery waste heat, after cooling to 350 DEG C enter efficiently humidification washer (9) carry out acid-scrubbing cleaning.Into sky
Hot-air a part of air preheater (6) comes from the normal temperature air that cold air blower (7) are sucked from atmosphere, and another part comes from
The high temperature air that air preheater (6) outlet returns；It is returned with the hot-air a part for being warming up to 500 DEG C after high-temperature flue gas heat exchange
To hot-air blower (8), a part enters pyrolysis furnace (4) and is used as combustion air.
4. closing acid-scrubbing cleaning
High-temperature flue gas from air preheater (6) initially enters efficiently humidification washer (9), the flue gas in washer
Substantially cool down by adiabatic humidification process and remove most flue dust and impurity and phosphoric acid, subsequently into filling cooling tower
(10), further cooling, dedusting and remove NOx.The flue gas cool-down of filling cooling tower is to 37 DEG C out, then purified electrostatic precipitator (11)
Acid mist is removed, sulphuric acid mist content is down to 3mg/m in exiting flue gas3Afterwards, it then fills into after partial air and is sent into drying tower (13) and is done
It is dry.
5. converting, absorbing twice twice
From drying tower (13) come out cleaning, dry flue gas through main blower (24) boost after, into heat exchanger (25,26)
Shell side heat exchange, enters converter (28) after being warming up to 420 DEG C, and the sulfur dioxide in flue gas is at (28) first, second and third sections of converter
It is reacted under the action of catalyst with oxygen and generates sulfur trioxide, the high-temperature flue gas after reaction is sent into heat exchanger (26,31,25) tube side
Low-temperature flue gas heat exchange with shell side cools to 170 DEG C and enters the first absorption tower (14) absorption sulfur trioxide；From the first absorption tower
(14) come out flue gas be warming up to 420 DEG C through heat exchanger (29,31) after enter converter (28), under four sections of catalyst actions into
Row reaction, the flue gas after reaction heating be sent into the low-temperature flue gas heat exchange of heat exchanger (30) tube side and shell side to after 410 DEG C again into
Enter converter (28), the reaction was continued under five sections of catalyst actions, enters the low temperature cigarette of heat exchanger (29) tube side and shell side later
Gas heat exchange, after cooling to 140 DEG C enter second absorption tower (15) double absorption sulfur trioxide, absorption tower (14,15) generate at
Product sulfuric acid respectively enters a suction tower circulating slot (17) and two and inhales tower circulating slot (18), then through finished acid underground tank (19) and finished product
Sour tank (20) goes acetylene cleaning device to reuse.
6. vent gas treatment
The absorption tail gas of second absorption tower (15) discharge inhales tower (23) sodium hydroxide lye spray-absorption remnants bis- by tail
Sulfur oxide, then discharged after two-stage tail inhales electrostatic precipitator (12) demisting, exhaust emissions concentration can achieve SO2 40mg/m3, Nox
40mg/m3, 3 mg/m of acid mist3, it is far below national standard.
Embodiment 2
1. Pintsch process
Combustion in pyrolysis furnace (4) is sprayed into after being first sufficiently mixed liquefied gas and 550 DEG C of hot-air in burner (3)
It burns, maintains furnace temperature at 1050 DEG C.Then acetylene cleaning Waste Sulfuric Acid is boosted into 0.35MPa by spent acid pump (1), with compressed air
Progress Pintsch process reaction in pyrolysis furnace is sprayed into after being passed through spent acid spray gun (2) atomization together, is ultimately generated containing sulfur dioxide, three oxygen
Change the high-temperature flue gas of sulphur, phosphorus pentoxide, carbon dioxide, water, nitrogen, flue dust etc..
2. furnace gas is cooling
High-temperature flue gas comes out from pyrolysis furnace (4) and initially enters natural cooling in burner-gas cooler (5), tentatively cools to 750
DEG C or more after enter air preheater (6), the flue dust to settle down and molten state salt are discharged by burner-gas cooler ash bucket.
3. air preheat
High-temperature flue gas from burner-gas cooler (5) enters 550 that air preheater (6) and hot-air blower (8) are sent
DEG C hot-air heat exchange, recovery waste heat, after cooling to 375 DEG C enter efficiently humidification washer (9) carry out acid-scrubbing cleaning.Into sky
Hot-air a part of air preheater (6) comes from the normal temperature air that cold air blower (7) are sucked from atmosphere, and another part comes from
The high temperature air that air preheater (6) outlet returns；It is returned with the hot-air a part for being warming up to 550 DEG C after high-temperature flue gas heat exchange
To hot-air blower (8), a part enters pyrolysis furnace (4) and is used as combustion air.
4. closing acid-scrubbing cleaning
High-temperature flue gas from air preheater (6) initially enters efficiently humidification washer (9), the flue gas in washer
Substantially cool down by adiabatic humidification process and remove most flue dust and impurity and phosphoric acid, subsequently into filling cooling tower
(10), further cooling, dedusting and remove NOx.The flue gas cool-down of filling cooling tower is to 37 DEG C out, then purified electrostatic precipitator (11)
Acid mist is removed, sulphuric acid mist content is down to 3.5mg/m in exiting flue gas3Afterwards, then after filling into partial air it is sent into drying tower (13) progress
It is dry.
5. converting, absorbing twice twice
From drying tower (13) come out cleaning, dry flue gas through main blower (24) boost after, into heat exchanger (25,26)
Shell side heat exchange, enters converter (28) after being warming up to 420 DEG C, and the sulfur dioxide in flue gas is at (28) first, second and third sections of converter
It is reacted under the action of catalyst with oxygen and generates sulfur trioxide, the high-temperature flue gas after reaction is sent into heat exchanger (26,31,25) tube side
Low-temperature flue gas heat exchange with shell side cools to 170 DEG C and enters the first absorption tower (14) absorption sulfur trioxide；From the first absorption tower
(14) come out flue gas be warming up to 420 DEG C through heat exchanger (29,31) after enter converter (28), under four sections of catalyst actions into
Row reaction, the flue gas after reaction heating be sent into the low-temperature flue gas heat exchange of heat exchanger (30) tube side and shell side to after 410 DEG C again into
Enter converter (28), the reaction was continued under five sections of catalyst actions, enters the low temperature cigarette of heat exchanger (29) tube side and shell side later
Gas heat exchange, after cooling to 140 DEG C enter second absorption tower (15) double absorption sulfur trioxide, absorption tower (14,15) generate at
Product sulfuric acid respectively enters a suction tower circulating slot (17) and two and inhales tower circulating slot (18), then through finished acid underground tank (19) and finished product
Sour tank (20) goes acetylene cleaning device to reuse.
6. vent gas treatment
The absorption tail gas of second absorption tower (15) discharge inhales tower (23) sodium hydroxide lye spray-absorption remnants bis- by tail
Sulfur oxide, then discharged after two-stage tail inhales electrostatic precipitator (12) demisting, exhaust emissions concentration can achieve SO2 42mg/m3, Nox
42mg/m3, acid mist 3.5mg/m3, it is far below national standard.
Embodiment 3
1. Pintsch process
Combustion in pyrolysis furnace (4) is sprayed into after being first sufficiently mixed sour gas and 600 DEG C of hot-air in burner (3)
It burns, maintains furnace temperature at 1100 DEG C.Then acetylene cleaning Waste Sulfuric Acid is boosted into 0.4MPa by spent acid pump (1), with compressed air
Progress Pintsch process reaction in pyrolysis furnace is sprayed into after being passed through spent acid spray gun (2) atomization together, is ultimately generated containing sulfur dioxide, three oxygen
Change the high-temperature flue gas of sulphur, phosphorus pentoxide, carbon dioxide, water, nitrogen, flue dust etc..
2. furnace gas is cooling
High-temperature flue gas comes out from pyrolysis furnace (4) and initially enters natural cooling in burner-gas cooler (5), tentatively cools to 800
DEG C or more after enter air preheater (6), the flue dust to settle down and molten state salt are discharged by burner-gas cooler ash bucket.
3. air preheat
High-temperature flue gas from burner-gas cooler (5) enters 600 that air preheater (6) and hot-air blower (8) are sent
DEG C hot-air heat exchange, recovery waste heat, after cooling to 400 DEG C enter efficiently humidification washer (9) carry out acid-scrubbing cleaning.Into sky
Hot-air a part of air preheater (6) comes from the normal temperature air that cold air blower (7) are sucked from atmosphere, and another part comes from
The high temperature air that air preheater (6) outlet returns；It is returned with the hot-air a part for being warming up to 600 DEG C after high-temperature flue gas heat exchange
To hot-air blower (8), a part enters pyrolysis furnace (4) and is used as combustion air.
4. closing acid-scrubbing cleaning
High-temperature flue gas from air preheater (6) initially enters efficiently humidification washer (9), the flue gas in washer
Substantially cool down by adiabatic humidification process and remove most flue dust and impurity and phosphoric acid, subsequently into filling cooling tower
(10), further cooling, dedusting and remove NOx.The flue gas cool-down of filling cooling tower is to 38 DEG C out, then purified electrostatic precipitator (11)
Acid mist is removed, sulphuric acid mist content is down to 4.0mg/m in exiting flue gas3Afterwards, then after filling into partial air it is sent into drying tower (13) progress
It is dry.
5. converting, absorbing twice twice
From drying tower (13) come out cleaning, dry flue gas through main blower (24) boost after, into heat exchanger (25,26)
Shell side heat exchange, enters converter (28) after being warming up to 420 DEG C, and the sulfur dioxide in flue gas is at (28) first, second and third sections of converter
It is reacted under the action of catalyst with oxygen and generates sulfur trioxide, the high-temperature flue gas after reaction is sent into heat exchanger (26,31,25) tube side
Low-temperature flue gas heat exchange with shell side cools to 170 DEG C and enters the first absorption tower (14) absorption sulfur trioxide；From the first absorption tower
(14) come out flue gas be warming up to 420 DEG C through heat exchanger (29,31) after enter converter (28), under four sections of catalyst actions into
Row reaction, the flue gas after reaction heating be sent into the low-temperature flue gas heat exchange of heat exchanger (30) tube side and shell side to after 410 DEG C again into
Enter converter (28), the reaction was continued under five sections of catalyst actions, enters the low temperature cigarette of heat exchanger (29) tube side and shell side later
Gas heat exchange, after cooling to 140 DEG C enter second absorption tower (15) double absorption sulfur trioxide, absorption tower (14,15) generate at
Product sulfuric acid respectively enters a suction tower circulating slot (17) and two and inhales tower circulating slot (18), then through finished acid underground tank (19) and finished product
Sour tank (20) goes acetylene cleaning device to reuse.
6. vent gas treatment
The absorption tail gas of second absorption tower (15) discharge inhales tower (23) sodium hydroxide lye spray-absorption remnants bis- by tail
Sulfur oxide, then discharged after two-stage tail inhales electrostatic precipitator (12) demisting, exhaust emissions concentration can achieve SO2 45mg/m3, Nox
45mg/m3, acid mist 4.0mg/m3, it is far below national standard.
Embodiment 4
1. Pintsch process
Pyrolysis furnace is sprayed into after being first sufficiently mixed natural gas, sour gas and 650 DEG C of hot-air in burner (3)
(4) burning in, maintains furnace temperature at 1150 DEG C.Then acetylene cleaning Waste Sulfuric Acid is boosted into 0.45MPa by spent acid pump (1), with
Compressed air sprays into progress Pintsch process reaction in pyrolysis furnace after being passed through spent acid spray gun (2) atomization together, ultimately generates containing dioxy
Change the high-temperature flue gas of sulphur, sulfur trioxide, phosphorus pentoxide, carbon dioxide, water, nitrogen, flue dust etc..
2. furnace gas is cooling
High-temperature flue gas comes out from pyrolysis furnace (4) and initially enters natural cooling in burner-gas cooler (5), tentatively cools to 800
DEG C or more after enter air preheater (6), the flue dust to settle down and molten state salt are discharged by burner-gas cooler ash bucket.
3. air preheat
High-temperature flue gas from burner-gas cooler (5) enters 650 that air preheater (6) and hot-air blower (8) are sent
DEG C hot-air heat exchange, recovery waste heat, after cooling to 425 DEG C enter efficiently humidification washer (9) carry out acid-scrubbing cleaning.Into sky
Hot-air a part of air preheater (6) comes from the normal temperature air that cold air blower (7) are sucked from atmosphere, and another part comes from
The high temperature air that air preheater (6) outlet returns；It is returned with the hot-air a part for being warming up to 650 DEG C after high-temperature flue gas heat exchange
To hot-air blower (8), a part enters pyrolysis furnace (4) and is used as combustion air.
4. closing acid-scrubbing cleaning
High-temperature flue gas from air preheater (6) initially enters efficiently humidification washer (9), the flue gas in washer
Substantially cool down by adiabatic humidification process and remove most flue dust and impurity and phosphoric acid, subsequently into filling cooling tower
(10), further cooling, dedusting and remove NOx.The flue gas cool-down of filling cooling tower is to 38 DEG C out, then purified electrostatic precipitator (11)
Acid mist is removed, sulphuric acid mist content is down to 4.5mg/m in exiting flue gas3Afterwards, then after filling into partial air it is sent into drying tower (13) progress
It is dry.
5. converting, absorbing twice twice
From drying tower (13) come out cleaning, dry flue gas through main blower (24) boost after, into heat exchanger (25,26)
Shell side heat exchange, enters converter (28) after being warming up to 420 DEG C, and the sulfur dioxide in flue gas is at (28) first, second and third sections of converter
It is reacted under the action of catalyst with oxygen and generates sulfur trioxide, the high-temperature flue gas after reaction is sent into heat exchanger (26,31,25) tube side
Low-temperature flue gas heat exchange with shell side cools to 170 DEG C and enters the first absorption tower (14) absorption sulfur trioxide；From the first absorption tower
(14) come out flue gas be warming up to 420 DEG C through heat exchanger (29,31) after enter converter (28), under four sections of catalyst actions into
Row reaction, the flue gas after reaction heating be sent into the low-temperature flue gas heat exchange of heat exchanger (30) tube side and shell side to after 410 DEG C again into
Enter converter (28), the reaction was continued under five sections of catalyst actions, enters the low temperature cigarette of heat exchanger (29) tube side and shell side later
Gas heat exchange, after cooling to 140 DEG C enter second absorption tower (15) double absorption sulfur trioxide, absorption tower (14,15) generate at
Product sulfuric acid respectively enters a suction tower circulating slot (17) and two and inhales tower circulating slot (18), then through finished acid underground tank (19) and finished product
Sour tank (20) goes acetylene cleaning device to reuse.
6. vent gas treatment
The absorption tail gas of second absorption tower (15) discharge inhales tower (23) sodium hydroxide lye spray-absorption remnants bis- by tail
Sulfur oxide, then discharged after two-stage tail inhales electrostatic precipitator (12) demisting, exhaust emissions concentration can achieve SO2 47mg/m3, Nox
47mg/m3, acid mist 4.5mg/m3, it is far below national standard.
Embodiment 5
1. Pintsch process
Pyrolysis furnace (4) are sprayed into after being first sufficiently mixed liquefied gas, molten sulfur and 700 DEG C of hot-air in burner (3)
Middle burning maintains furnace temperature at 1150 DEG C.Then acetylene cleaning Waste Sulfuric Acid is boosted into 0.5MPa by spent acid pump (1), with compression
Air be passed through together spent acid spray gun (2) atomization after spray into pyrolysis furnace in carry out Pintsch process reaction, ultimately generate containing sulfur dioxide,
The high-temperature flue gas of sulfur trioxide, phosphorus pentoxide, carbon dioxide, water, nitrogen, flue dust etc..
2. furnace gas is cooling
High-temperature flue gas comes out from pyrolysis furnace (4) and initially enters natural cooling in burner-gas cooler (5), tentatively cools to 800
DEG C or more after enter air preheater (6), the flue dust to settle down and molten state salt are discharged by burner-gas cooler ash bucket.
3. air preheat
High-temperature flue gas from burner-gas cooler (5) enters 700 that air preheater (6) and hot-air blower (8) are sent
DEG C hot-air heat exchange, recovery waste heat, after cooling to 450 DEG C enter efficiently humidification washer (9) carry out acid-scrubbing cleaning.Into sky
Hot-air a part of air preheater (6) comes from the normal temperature air that cold air blower (7) are sucked from atmosphere, and another part comes from
The high temperature air that air preheater (6) outlet returns；It is returned with the hot-air a part for being warming up to 700 DEG C after high-temperature flue gas heat exchange
To hot-air blower (8), a part enters pyrolysis furnace (4) and is used as combustion air.
4. closing acid-scrubbing cleaning
High-temperature flue gas from air preheater (6) initially enters efficiently humidification washer (9), the flue gas in washer
Substantially cool down by adiabatic humidification process and remove most flue dust and impurity and phosphoric acid, subsequently into filling cooling tower
(10), further cooling, dedusting and remove NOx.The flue gas cool-down of filling cooling tower is to 38 DEG C out, then purified electrostatic precipitator (11)
Acid mist is removed, sulphuric acid mist content is down to 5.0mg/m in exiting flue gas3Afterwards, then after filling into partial air it is sent into drying tower (13) progress
It is dry.
5. converting, absorbing twice twice
From drying tower (13) come out cleaning, dry flue gas through main blower (24) boost after, into heat exchanger (25,26)
Shell side heat exchange, enters converter (28) after being warming up to 420 DEG C, and the sulfur dioxide in flue gas is at (28) first, second and third sections of converter
It is reacted under the action of catalyst with oxygen and generates sulfur trioxide, the high-temperature flue gas after reaction is sent into heat exchanger (26,31,25) tube side
Low-temperature flue gas heat exchange with shell side cools to 170 DEG C and enters the first absorption tower (14) absorption sulfur trioxide；From the first absorption tower
(14) come out flue gas be warming up to 420 DEG C through heat exchanger (29,31) after enter converter (28), under four sections of catalyst actions into
Row reaction, the flue gas after reaction heating be sent into the low-temperature flue gas heat exchange of heat exchanger (30) tube side and shell side to after 410 DEG C again into
Enter converter (28), the reaction was continued under five sections of catalyst actions, enters the low temperature cigarette of heat exchanger (29) tube side and shell side later
Gas heat exchange, after cooling to 140 DEG C enter second absorption tower (15) double absorption sulfur trioxide, absorption tower (14,15) generate at
Product sulfuric acid respectively enters a suction tower circulating slot (17) and two and inhales tower circulating slot (18), then through finished acid underground tank (19) and finished product
Sour tank (20) goes acetylene cleaning device to reuse.
6. vent gas treatment
The absorption tail gas of second absorption tower (15) discharge inhales tower (23) sodium hydroxide lye spray-absorption remnants bis- by tail
Sulfur oxide, then discharged after two-stage tail inhales electrostatic precipitator (12) demisting, exhaust emissions concentration can achieve SO2 50mg/m3, Nox
50mg/m3, acid mist 5.0mg/m3, it is far below national standard.
Claims (8)
1. a kind of regeneration technology of acetylene cleaning Waste Sulfuric Acid, it is characterised in that: raw material is made with acetylene cleaning Waste Sulfuric Acid, by fuel and
Oxygen-containing gas is sprayed into pyrolysis furnace by burner to burn, and heat needed for providing cracking reaction will after reaching reaction temperature
Acetylene cleaning Waste Sulfuric Acid sprays into pyrolysis furnace after being atomized by spent acid spray gun and carries out cracking reaction, makes acetylene Waste Sulfuric Acid in pyrolysis furnace
Generate containing sulfur dioxide, sulfur trioxide, oxygen, phosphorus pentoxide, carbon dioxide, water vapour, nitrogen, flue dust high-temperature flue gas,
High-temperature flue gas through furnace gas cooling, air preheat, closing acid-scrubbing cleaning, drying, twice conversion, twice absorb process after produce qualification
Finished product sulfuric acid, relieving haperacidity tail gas after spray-absorption and electric demisting by discharging；Spent acid cracking reaction temperature is >=800 DEG C；Cracking
Oxygen mole concentration in outlet of still flue gas is 0 ~ 10%；Sulfur dioxide molar concentration >=4%；The high-temperature flue gas for cracking outlet of still is first
First need to cool down >=700 DEG C, the cooling equipment used is burner-gas cooler.
2. the regeneration technology of acetylene cleaning Waste Sulfuric Acid according to claim 1, it is characterised in that: acetylene cleaning sulfur waste acid regeneration
The primary raw material of technique be containing sulfuric acid, water, organic matter, phosphoric acid, inorganic salts acetylene cleaning Waste Sulfuric Acid, acetylene cleaning Waste Sulfuric Acid
In sulfuric acid content >=70%；The fuel includes: natural gas, liquefied petroleum gas, sulphur, sour gas, dry gas, hydrogenolysis gassing, light
It is one or more of in matter oil, mink cell focus；The oxygen-containing gas be air, oxygen-enriched air or other contain the gas of oxygen, it is oxygen-containing
The charging temperature of gas is room temperature or more.
3. the regeneration technology of acetylene cleaning Waste Sulfuric Acid according to claim 1, it is characterised in that: burner-gas cooler includes heat dissipation
Pipe and ash bucket；The material of burner-gas cooler is high-alloy steel resistant to high temperature or silicon carbide.
4. the regeneration technology of acetylene cleaning Waste Sulfuric Acid according to claim 1, it is characterised in that: come out from burner-gas cooler
High-temperature flue gas enters air preheater and exchanges heat with the hot-air that hot-air blower is sent, and enters efficiently humidification after recycling thermal energy
Washer carries out acid-scrubbing cleaning；Into air preheater hot-air a part sucked from atmosphere from cold air blower it is normal
Warm air, the high temperature air that another part is returned from air preheater outlet are sent into after the two mixing by hot-air blower
Air preheater；High temperature air a part of air preheater outlet returns to hot-air blower, and a part enters pyrolysis furnace and makees
For combustion air.
5. the regeneration technology of acetylene cleaning Waste Sulfuric Acid according to claim 4, it is characterised in that: the cigarette of air preheater outlet
Temperature degree >=400 DEG C；Air themperature >=300 DEG C of air preheater import.
6. the regeneration technology of acetylene cleaning Waste Sulfuric Acid according to claim 4, it is characterised in that: come out from air preheater
High-temperature flue gas initially enters efficiently humidification washer and carries out adiabatic humidification cooling and clean, further subsequently into filling cooling tower
Cooling dedusting and NOx, the flue gas of filling cooling tower goes drying tower to be dried after purified electrostatic precipitator removes acid mist again out.
7. the regeneration technology of acetylene cleaning Waste Sulfuric Acid according to claim 6, it is characterised in that: the system of second absorption tower outlet
Sour tail gas inhales sulfur dioxide remaining in tower absorbing liquid spray-absorption tail gas through tail first, then inhales electrostatic precipitator through two-stage tail and removes
It is discharged after removing acid mist, exhaust emissions concentration reaches SO2≤50mg/m3, Nox≤50mg/m3, acid mist≤5mg/m3。
8. the regeneration technology of acetylene cleaning Waste Sulfuric Acid according to claim 7, it is characterised in that: absorbing liquid is water-soluble using alkalinity
Liquid or hydrogen peroxide.
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| CN107265410A (en) * | 2017-07-03 | 2017-10-20 | 成都世远科技有限公司 | The high temperature purification technique of containing sulfate Waste Sulfuric Acid in Waste Sulfuric Acid recycled product sulfuric acid process |
| CN107934920A (en) * | 2017-11-29 | 2018-04-20 | 中石化南京工程有限公司 | A kind of device of Waste Sulfuric Acid and hydrogen sulfide waste gas integrated treatment |
| CN107954403B (en) * | 2018-01-08 | 2024-03-12 | 上海乐谦工程科技有限公司 | Resource-saving waste acid treatment process and device |
| CN109052332B (en) * | 2018-10-24 | 2022-02-22 | 泰兴锦汇化工有限公司 | Method for preparing chlorosulfonic acid by regenerating high-COD (chemical oxygen demand) saline dilute acid |
| CN109603700A (en) * | 2018-11-27 | 2019-04-12 | 中国成达工程有限公司 | Utilize calcium carbide Slag treatment acetylene cleaning Waste Sulfuric Acid technique and device |
| CN110894064A (en) * | 2019-12-24 | 2020-03-20 | 美景（北京）环保科技有限公司 | Device and method for preparing sulfuric acid by cracking and regenerating waste sulfuric acid and/or sulfur-containing waste liquid |
| CN111888831A (en) * | 2020-06-24 | 2020-11-06 | 刘发业 | Waste sulfuric acid recovery processing device and application thereof |
| CN115321491A (en) * | 2022-07-06 | 2022-11-11 | 宜宾海丰和锐有限公司 | Method for continuously treating odor of acetylene-cleaning waste sulfuric acid |
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| CN1751984A (en) * | 2004-09-20 | 2006-03-29 | 中国石油天然气股份有限公司 | Process for producing sulfuric acid by high-temperature cracking of alkylation waste sulfuric acid |
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| CN1751984A (en) * | 2004-09-20 | 2006-03-29 | 中国石油天然气股份有限公司 | Process for producing sulfuric acid by high-temperature cracking of alkylation waste sulfuric acid |
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