CN214087722U - System for coking desulfurization waste liquid system sulphuric acid - Google Patents
System for coking desulfurization waste liquid system sulphuric acid Download PDFInfo
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- CN214087722U CN214087722U CN202022432179.1U CN202022432179U CN214087722U CN 214087722 U CN214087722 U CN 214087722U CN 202022432179 U CN202022432179 U CN 202022432179U CN 214087722 U CN214087722 U CN 214087722U
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Abstract
The utility model discloses a system for coking desulfurization waste liquid system sulphuric acid belongs to the environmental protection field. The system comprises an incinerator, a reactor and a sulfuric acid steam condenser, wherein fuel and desulfurization waste liquid are conveyed to the incinerator, the output end of the incinerator is sequentially connected with a heat recovery system and a dust remover, and the output end of the dust remover is sequentially connected with a tail gas treatment tower through the reactor, the sulfuric acid steam condenser and the tail gas treatment tower. By adopting the system, the problem that dilute acid is difficult to treat due to the fact that the process gas is washed and purified by the dilute acid in the prior art is solved, and the acid making device has the characteristics of short process flow, small equipment quantity, small occupied area of a production device, low energy consumption, high heat recovery rate and low operation cost.
Description
Technical Field
The utility model relates to an environmental protection field, concretely relates to system for sulphuric acid is made to coking desulfurization waste liquid.
Background
At present, all the production processes in the domestic coking industry are provided with desulfurization devices, sulfur elements in the technological process are recovered, waste liquid containing sulfur, ammonium salt and other substances can be by-produced in the production processes of the desulfurization devices, and the waste liquid can also cause environmental pollution if directly discharged.
In the prior art, the desulfurization waste liquid is treated by adopting an incineration method, and the incinerated desulfurization waste liquid contains SO2The gas is purified and dedusted by dilute sulfuric acid, the dust-containing dilute sulfuric acid generated in the purification process cannot be digested by an acid making device and cannot be effectively utilized by a coking plant, and when the process gas is purified by the dilute sulfuric acid, a low-temperature washing process is adopted, the temperature of the process gas is remarkably reduced (the temperature is reduced to more than 200 ℃), the temperature of the dilute acid is increased from about 50 ℃ to about 60 ℃, the dilute acid can only be cooled by circulating water, and the heat is difficult to be effectively utilized. In the prior art, the process gas which is purified to contain SO2 and moisture is treated by a production process of 2-to-2 absorption to generate sulfuric acid. The specific method comprises cleaning the cleaned product to contain SO2The process gas with moisture is sent into a drying device to remove moisture, the temperature of the process gas at the outlet of the drying device is usually about 50 ℃ and does not reach SO2Conversion to SO3The required reaction temperature needs to be the cold process gas entering the converter and heated by the hot process gas heated after the conversion reaction, the process gas is heated to the reaction temperature of over 380 ℃, then the conversion reaction is completed under the action of the catalyst in the converter, and part of SO is converted2Oxidation to SO3The gas temperature is raised after reaction, and the gas is sent into an absorption tower after heat exchange with cold process gas by a heat exchanger, and SO in the process gas is absorbed in the tower in a large amount of sulfuric acid circulation mode3Absorption of SO3The temperature of the post-circulating acid is raised, the post-circulating acid is cooled by circulating water, the temperature of the process gas is reduced to 80 ℃ after the primary absorption, the process gas is heated to the reaction temperature by a heat exchanger and then sent to a converter for secondary conversion, and the residual SO is converted2Oxidation to SO3And after heat exchange and temperature reduction, performing secondary absorption by using another absorption tower. The treatment process has the advantages of long flow, more equipment, large occupied area, high operation cost, large consumption of electric power and circulating water, low heat recovery rate in the process and ineffective utilization of a byproduct, namely dilute sulfuric acid.
SUMMERY OF THE UTILITY MODEL
The utility model provides a system for coking desulfurization waste liquid production sulphuric acid to above-mentioned prior art, effectively utilize the sulphur element in the desulfurization waste liquid, reduce the pollution of coking device accessory substance to the environment. Meanwhile, the process flow is short, the equipment is few, the occupied area is small, the heat recovery efficiency of the process is high, the operation cost is low, and the by-product dilute sulfuric acid is not produced.
The purpose of the utility model can be realized by the following technical scheme:
a method for preparing sulfuric acid from coking desulfurization waste liquid comprises the following steps:
(1) spraying gas or liquid fuel into the incinerator for combustion to generate high-temperature gas, then spraying the coking desulfurization waste liquid into the high-temperature gas environment in the incinerator, oxidizing and decomposing sulfur, ammonium salt and organic matters in the desulfurization waste liquid, and finally forming SO containing 900-1200 ℃ in the incinerator2，CO2，N2，O2，H2O high temperature process gas;
the main reaction is as follows:
S+O2＝SO2
NH4CNS+3O2＝2H2O+N2+SO2+CO2
(NH4)2S2O3+2.5O2＝4H2O+N2+2SO2
(NH4)2SO4+O2＝4H2O+N2+SO2
(2) the high-temperature process gas discharged from the incinerator passes through a heat recovery system heat exchanger, the heat of the process gas is used for generating steam or heating other media, and the temperature of the process gas discharged from the heat exchanger is reduced to 390-450 ℃;
(3) the process gas cooled to 390-450 ℃ enters a dust remover, and is directly filtered and dedusted, and the temperature of the process gas after dedusting is still maintained above the temperature required by catalytic oxidation;
(4) the dedusted process gas enters a reactor, and SO in the process gas is generated under the action of a catalyst2Further oxidized to SO3And has a part of SO3Reacting with water vapor to generate sulfuric acid vapor, performing oxidation reaction and sulfuric acid generation reaction both in an exothermic reaction, and recovering heat in the reactorThe system heat exchanger is used for recovering reaction heat to generate steam or heat other media, and the temperature of the process gas discharged from the reactor is controlled to be 290 +/-20 ℃;
SO2+1/2O2＝SO3
H2o (steam) + SO3＝H2SO4(Car)
(5) The process gas leaving the reactor enters a sulfuric acid steam condenser, the process gas is cooled by air, sulfuric acid steam in the process gas is condensed, and residual SO3Continuously reacting with water vapor to generate sulfuric acid vapor and finally condensing into liquid sulfuric acid; the process gas leaving the sulfuric acid vapor condenser still contains very little SO2And then enters a tail gas treatment system, and is discharged after reaching the standard after being treated.
The method comprises the following steps: the air in the step (5) is pressurized by an air fan and then is sent into a sulfuric acid steam condenser to cool the process gas, the temperature of the air is increased after heat exchange, the hot air at the outlet of the sulfuric acid steam condenser is divided into two parts, wherein one part is used as combustion-supporting air of the incinerator, the part of air is sent into a process gas-air heat exchanger of a heat recovery system heat exchanger, the process gas with higher temperature is used for heating the part of combustion-supporting air, the temperature is raised again and then the part of air is sent into the incinerator, and the fuel consumption of the incinerator is reduced; and the rest air is sent into a feed water heater of the heat recovery system, the feed water sent into the heat recovery system is preheated, and the air is directly discharged after heat exchange and temperature reduction.
The method comprises the following steps: the heat exchanger of the heat recovery system consists of an evaporator I arranged at the outlet of the incinerator, an air heat exchanger, a steam superheater and an evaporator II arranged in the reactor, a feed water heater, a steam drum and steam-water pipelines connected with the devices, the heat in the acid making process is recovered to generate steam, the heat recovery system can also adopt heat conduction oil or molten salt as a heat conduction medium, and the recovered heat can also generate steam or heat other process materials.
In some specific embodiments: feeding water from the outside, preheating the feeding water to 180 +/-50 ℃ by using hot air through a water feeding heater, feeding the feeding water into a steam drum to be mixed with furnace water, wherein the furnace water in the steam drum respectively flows into an evaporator I at an outlet of an incinerator and an evaporator II arranged in a reactor, the furnace water in the evaporator I and the evaporator II is partially evaporated by heating to generate a steam-water mixture, the steam-water mixture reflows to the steam drum under the action of thermosiphon, steam is separated from the furnace water in the steam drum, the furnace water continuously enters the evaporator I and the evaporator II to circulate, and medium-pressure saturated steam is separated out from the steam drum; the saturated steam is sent into the reactor again and is provided with a steam superheater, and the saturated steam is heated by the process gas and is externally supplied to the medium-pressure superheated steam.
The method comprises the following steps: the water content of the desulfurization waste liquid is more than 40 percent.
The method comprises the following steps: the system for preparing sulfuric acid from coking desulfurization waste liquid comprises an incinerator, a reactor and a sulfuric acid steam condenser, wherein fuel and desulfurization waste liquid are conveyed to the incinerator, the output end of the incinerator is sequentially connected with a heat recovery system and a dust remover, and the output end of the dust remover is sequentially connected with a tail gas treatment tower through the reactor, the sulfuric acid steam condenser and the tail gas treatment tower.
The method comprises the following steps: the heat recovery system comprises an evaporator I arranged at the outlet of the incinerator, the evaporator I is connected with a process gas-air heat exchanger, a water supply output pipeline is connected with a steam drum after passing through a water supply heater, one output end of the steam drum is connected with the steam drum through the evaporator I, and the other output end of the steam drum is connected with the steam drum through an evaporator II.
The method comprises the following steps: air is conveyed to a sulfuric acid steam condenser through an air fan, the output end of the sulfuric acid steam condenser is divided into two branches, one branch is conveyed to a feed water heater, and the other branch is connected with an incinerator through a process gas-air heat exchanger.
SO in reactor2Oxidation to SO3，S03And H20 reaction produces sulphuric acid and is exothermic reaction, the utility model discloses among the technical scheme: two or more catalyst beds are arranged in the reactor, heat exchange equipment of a heat recovery system is arranged at the outlets of the two catalyst beds, interlayer process gas is cooled, heat generated in the reaction process is recovered, and the catalytic oxidation reaction process is promoted. Preferably, the method comprises the following steps: the reactor is provided with 2 catalyst layers, a steam superheater is arranged below the upper catalyst layer, and an evaporation superheater is arranged below the lower catalyst layerAnd (II) a device. The heat recovery system heat exchanger equipment is used for recovering reaction heat and pushing the reaction process, and more than 99 percent of SO in the final process gas2Are uniformly oxidized into SO3And the temperature of the process gas at the outlet of the reactor is controlled to be 290 ℃ plus or minus 20 ℃.
The utility model discloses among the technical scheme: the catalyst includes, but is not limited to, vanadium pentoxide.
The utility model discloses among the technical scheme: the pressure is gauge pressure.
The utility model has the advantages that:
the method for producing sulfuric acid by treating coking desulfurization waste liquid in an incineration mode enables sulfur elements to be effectively utilized, the generated product is wide in application, and environmental pollution caused by direct discharge of the desulfurization waste liquid is avoided. The utility model discloses a method of cooling to 390 ~ 450 ℃ process gas filtration dust removal after burning, the secondary pollutant is avoided appearing to the not by-product dusty dilute acid. The utility model adopts the dust-removing device containing SO2The process gas with water directly enters a reactor to react SO2Oxidation to SO3，SO3Then reacts with water vapor to generate sulfuric acid vapor, and finally is condensed to generate sulfuric acid, the process gas drying flow in the prior art is not needed, the heat exchange flow that the process gas is heated and then sent to a converter for reaction in the prior art is not needed, and a large amount of circulating acid is not needed to absorb SO in an absorption tower3The absorption process of (1). Therefore, the utility model discloses shorten process flow greatly than prior art, processing equipment quantity obviously reduces, and the production device area also correspondingly reduces, need not use a large amount of circulating water and circulation acid, and the energy consumption is showing and is reducing, and the running cost reduces, and the technological process calorific loss reduces, and the rate of heat recovery promotes by a wide margin, and the byproduct steam volume obviously increases.
Drawings
Fig. 1 is a schematic diagram of the system for preparing sulfuric acid from coking desulfurization waste liquid.
Wherein: 1. a desulfurization waste liquid pump 2, an incinerator 3, a heat recovery system 4, a dust remover 5, a reactor 6, a sulfuric acid steam condenser 7, an air fan 8, a tail absorption circulating pump 9 and a tail gas treatment tower;
heat recovery system apparatus
3-1 evaporator I, 3-2 process gas-air heat exchanger, 3-3 water supply heater, 3-4 steam drum, 3-5 steam superheater and 3-6 evaporator II.
Detailed Description
The present invention will be further explained with reference to the following embodiments, but the scope of the present invention is not limited thereto:
referring to fig. 1, a system for preparing sulfuric acid from coking desulfurization waste liquid comprises an incinerator 2, a reactor 5 and a sulfuric acid vapor condenser 6, wherein fuel and desulfurization waste liquid are conveyed to the incinerator 2, the output end of the incinerator 2 is sequentially connected with a heat recovery system and a dust remover 4, and the output end of the dust remover 4 is sequentially connected with the reactor 5, the sulfuric acid vapor condenser 6 and a tail gas treatment tower 9.
The heat recovery system comprises an evaporator I3-1 arranged at the outlet of an incinerator 2, the evaporator I3-1 is connected with a process gas-air heat exchanger 3-2, a feed water output pipeline passes through a feed water heater 3-3 and then is connected with a steam drum 3-4, one output end of the steam drum 3-4 is connected with the steam drum 3-4 through an evaporator I3-1, and the other output end of the steam drum 3-4 is connected with the steam drum 3-4 through an evaporator II 3-6.
Air is conveyed to a sulfuric acid steam condenser 6 through an air fan 7, the output end of the sulfuric acid steam condenser 6 is divided into two branches, one branch is conveyed to a feed water heater 3-3, and the other branch is connected with an incinerator 2 through a process gas-air heat exchanger 3-2. The reactor 5 is provided with 2 catalyst layers, a steam superheater 3-5 is arranged below the upper catalyst layer, and an evaporator II3-6 is arranged below the lower catalyst layer.
A method for preparing sulfuric acid from coking desulfurization waste liquid by using the system comprises the following steps:
the composition of the desulfurized waste liquid is shown in the following table
The coke oven gas as by-product of the coking device is used as the treatment deviceThe fuel is burnt in the incinerator 2 to generate high-temperature gas, the temperature of a hearth is controlled to be about 900 ℃ to 1200 ℃, the coking desulfurization waste liquid is sprayed into the hearth, and sulfur, ammonium salt and organic matters in the coking desulfurization waste liquid are oxidized and decomposed into SO-containing substances in the high-temperature hearth2，CO2，N2，O2，H2The process gas is evaporated by a heat recovery system I3-1 and a process gas-air heat exchanger 3-2 to be cooled to 400 ℃, and then enters a dust remover 4, the process gas enters a reactor 5 after dust is removed, 2 layers of catalysts are arranged in the reactor 5, and SO in the process gas is2Partial oxidation to SO with a first layer of catalyst3The temperature of the process gas is raised to 600 ℃, the temperature is reduced to 400 ℃ through a steam superheater 3-5 of a heat recovery system arranged between layers, then the process gas enters a second layer of catalyst, and the residual SO in the process gas2Continued oxidation to SO3More than 99% of SO after passing through 2 layers of catalyst2Are uniformly oxidized into SO3The temperature of the second layer of the catalyst discharged from the process gas is raised to 520 ℃, and then is cooled to 300 ℃ through a heat recovery system evaporator II 3-6; the process gas is discharged from the reactor and enters a sulfuric acid steam condenser 6, the process gas in the condenser is cooled by air, the sulfuric acid steam is gradually condensed, and residual SO in the process gas3Then continuously reacting with water vapor to generate sulfuric acid vapor, and completely condensing the sulfuric acid vapor at the outlet of the condenser when the temperature of the process air is reduced to be below 150 ℃. The process gas after the sulfuric acid vapor condenser 6 is sent into a tail gas treatment tower, and the tail gas treatment tower 9 absorbs the residual SO in the process gas by adopting hydrogen peroxide2Clean dilute sulfuric acid with the concentration of about 20 percent is generated, and S0 in tail gas discharged from the tower2The content is less than 100mg/Nm3And the emission can reach the standard. The tail gas treatment tower generates 20% clean dilute sulfuric acid which is sent to a liquid sulfuric acid outlet of a condenser, and the concentration of the finished acid is adjusted.
The air is sent into the sulfuric acid steam condenser 6 after being boosted by the air fan 7, the temperature of the air of the cooling process gas is raised to 200 ℃, the hot air at the outlet of the sulfuric acid steam condenser 6 is divided into two parts, wherein one part is used as the combustion-supporting air of the incinerator 2, the part of air is sent into the process gas-air heat exchanger 3-2, the process gas with higher temperature is heated to 460 ℃ and then sent into the incinerator 2; and the rest air is fed into a feed water heater 3-3, the feed water of the heat recovery system at the temperature of 104 ℃ is heated to 160 ℃, and the air is directly discharged after heat exchange and temperature reduction.
The heat recovery system consists of an evaporator I3-1 arranged at the outlet of the incinerator, a process gas-air heat exchanger 3-2, a superheater 3-5 and an evaporator II3-6 arranged in the reactor, a steam drum 3-4, a water supply heater 3-3 and steam-water pipeline pipes connected with the devices. Feeding water of 104 ℃ from the outside, preheating the water to 160 ℃ by hot air through a feed water heater 3-3, feeding the water into a steam drum 3-4 to mix with furnace water, enabling the furnace water in the steam drum 3-4 to flow into an evaporator I3-1 and an evaporator II3-6, enabling the heated part of the furnace water to be evaporated to generate a steam-water mixture, enabling the steam-water mixture to flow back to the steam drum 3-4 under the action of thermosiphon, separating steam from the furnace water in the steam drum 3-4, continuously enabling the furnace water to enter the evaporator I3-1 and the evaporator II3-6 for circulation, and enabling the yield of the medium-pressure saturated steam with 6.0MPa separated from the steam drum 3-4 to reach 9.5 t/h; the saturated steam is sent into the reactor and is provided with a superheater 3-5, and the saturated steam is heated by the process gas to be supplied as 460 ℃ medium-pressure superheated steam.
The desulfurization waste liquid is treated by adopting the prior art and needs to be subjected to incineration, purification, conversion and dry absorption of 4 working sections, the number of process equipment is large, and the prior art of the same-scale treatment device is compared with the continuous operation electric equipment of the technology as follows:
| device name | Power of prior art electric device (kw) | Power of electric equipment (kw) |
| Waste liquid pump | 11 | 11 |
| Air blower | 37 | 132 |
| Dynamic wave circulating pump | 30 | ------- |
| Packed tower circulating pump | 15 | ------- |
| Drying circulating acid pump | 22 | ------- |
| One-suction circulation acid pump | 22 | ------- |
| Two-suction circulating acid pump | 22 | ------- |
| Tail suction circulating pump | 15 | 15 |
| SO2Blower fan | 160 | ------- |
| Total up to | 334 | 158 |
The power of the electric equipment in the technology is only 47% of that in the prior art, and the power consumption is correspondingly 47% of that in the prior art.
The dynamic wave circulating liquid in the purification process of the prior art needs to be cooled by circulating water, circulating acids in a drying tower, a first absorption tower and a second absorption tower need to be cooled by circulating water, the heat in the process is taken out and released to the atmosphere, 5t/h of desulfurization waste liquid is treated by the prior art, the consumption of the circulating water is 600t/h, and by adopting the technology, part of generated heat of sulfuric acid is recycled by a heat recovery system in a reactor to generate steam, and the other part of generated heat of the sulfuric acid is heated by air in a condenser without circulating cooling water, only a small amount of finished sulfuric acid at the outlet of the reactor needs to be cooled by circulating water, the consumption is 80t/h and is only 13% of the prior art.
In the prior art, a waste heat boiler is arranged behind an incinerator, process gas at 300 ℃ at a boiler outlet is directly cooled to 40 ℃ in a purification process by dilute acid, the reaction heat of a converter is used for heating the temperature of the process gas at the inlet of the converter, the absorption reaction heat of a dry absorption working section is also cooled by circulating water, the device with the same scale adopts 5.8MPa (g) saturated steam with the steam yield of 4.2t/h in the prior art, the steam yield can reach 9.5t/h in the prior art, the steam parameter is 5.8MPa (g), the superheated steam with the temperature of 460 ℃ is adopted, and the steam yield is 226% in the prior art.
Adopt the device of the prior art to treat the desulfurized waste liquid, the incineration workshop section occupies an area of 200m2And the floor area of the purification section is 230m2Dry suction tail suction working section occupying 310m3And the conversion section occupies 380m of land2Total device area 1120m2And does not include the floor space of the passage between the sections. The treatment device adopting the technology only needs a burning section (the floor area is 160 m)2) And a process gas treatment section (350 m)2)2 parts, the device is compact, and the total occupied area is 510m2It is only 45.5% of the prior art.
Claims (5)
1. The utility model provides a system for sulphuric acid is made to coking desulfurization waste liquid which characterized in that: the system comprises an incinerator (2), a reactor (5) and a sulfuric acid steam condenser (6), wherein fuel and desulfurization waste liquid are conveyed to the incinerator (2), the output end of the incinerator (2) is sequentially connected with a heat recovery system and a dust remover (4), and the output end of the dust remover (4) is sequentially connected with the reactor (5), the sulfuric acid steam condenser (6) and a tail gas treatment tower (9).
2. The system of claim 1, wherein: the heat recovery system comprises an evaporator I (3-1) arranged at the outlet of the incinerator (2), the evaporator I (3-1) is connected with a process gas-air heat exchanger (3-2), a water supply output pipeline is connected with a steam drum (3-4) after passing through a water supply heater (3-3), one output end of the steam drum (3-4) is connected with the steam drum (3-4) through the evaporator I (3-1), and the other output end of the steam drum is connected with the steam drum (3-4) through an evaporator II (3-6).
3. The system of claim 1, wherein: air is conveyed to a sulfuric acid steam condenser (6) through an air fan (7), the output end of the sulfuric acid steam condenser (6) is divided into two branches, one branch is conveyed to a feed water heater (3-3), and the other branch is connected with an incinerator (2) through a process gas-air heat exchanger (3-2).
4. The system of claim 1, wherein: two or more catalyst beds are arranged in the reactor, heat exchange equipment of a heat recovery system is arranged at outlets of the two catalyst beds, interlayer process gas is cooled, heat generated in the reaction process is recovered, and the catalytic oxidation reaction process is promoted.
5. The system of claim 4, wherein: the reactor is internally provided with 2 catalyst layers, a steam superheater (3-5) is arranged below the upper catalyst layer, and an evaporator II (3-6) is arranged below the lower catalyst layer.
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| CN114602299A (en) * | 2022-03-08 | 2022-06-10 | 太原理工大学 | Treatment process of coking desulfurization by-product |
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