CN112209351A - Method for preparing sulfuric acid from coking desulfurization waste liquid - Google Patents
Method for preparing sulfuric acid from coking desulfurization waste liquid Download PDFInfo
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- CN112209351A CN112209351A CN202011173873.4A CN202011173873A CN112209351A CN 112209351 A CN112209351 A CN 112209351A CN 202011173873 A CN202011173873 A CN 202011173873A CN 112209351 A CN112209351 A CN 112209351A
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- sulfuric acid
- incinerator
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 238000000034 method Methods 0.000 title claims abstract description 142
- 239000007788 liquid Substances 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 37
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 34
- 230000023556 desulfurization Effects 0.000 title claims abstract description 34
- 238000004939 coking Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000011084 recovery Methods 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000000428 dust Substances 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000010410 layer Substances 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 72
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/80—Apparatus
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/78—Preparation by contact processes characterised by the catalyst used
- C01B17/79—Preparation by contact processes characterised by the catalyst used containing vanadium
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for preparing sulfuric acid from coking desulfurization waste liquid, and belongs to the field of environmental protection. The method comprises the steps of feeding the coking desulfurization waste liquid into a high-temperature incinerator for decomposition to generate process gas, cooling the process gas by heat exchange equipment of a heat recovery system, feeding the cooled process gas into a dust removal system, and directly feeding the cooled process gas into a reactor for SO removal2Oxidation to SO3And part of SO3Reacting with water vapor in the process gas to generate sulfuric acid vapor, then feeding the process gas into a sulfuric acid vapor condenser, cooling and condensing after air cooling, and obtaining residual SO3And continuously reacting with water vapor to generate sulfuric acid vapor, condensing all sulfuric acid in the process gas at the outlet of the sulfuric acid vapor condenser, and treating the residual process gas by a tail gas tower treatment tower to reach the standard and discharge. The method solves the problem that the dilute acid generated by washing and purifying the process gas by the dilute acid in the prior art is difficult to treatThe acid making device has the characteristics of short process flow, small equipment quantity, small occupied area of the production device, low energy consumption, high heat recovery rate and low operation cost.
Description
Technical Field
The invention relates to the field of environmental protection, and particularly relates to a method for preparing sulfuric acid from 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.
Disclosure of Invention
The invention provides a method for producing sulfuric acid by coking desulfurization waste liquid aiming at the prior art, which effectively utilizes sulfur elements in the desulfurization waste liquid and reduces the pollution of byproducts of a coking device 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 invention 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 SO3The reaction with water vapor to generate sulfuric acid vapor, the oxidation reaction and the reaction for generating sulfuric acid are both exothermic reactions, a heat recovery system heat exchanger is arranged in the reactor, the reaction heat is recovered to generate steam or heat other media, and the temperature of process gas discharged from the reactor is controlled to be 290 ℃ plus or minus 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 preheater of a heat recovery system heat exchanger, the combustion-supporting air of the part is heated by the process gas with higher temperature, and the process gas is sent into the incinerator after being heated again, so that 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, a process gas-air preheater, a steam superheater and an evaporator II arranged in the reactor, a feedwater 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 preheater, 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 H2The sulfuric acid generated by the reaction of 0 is exothermic reaction, and the technical scheme of the invention is as follows: 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 catalyst is pushedAnd (4) oxidizing reaction progress. Preferably, the method comprises the following steps: the reactor is internally provided with 2 catalyst layers, a steam superheater is arranged below the upper catalyst layer, and an evaporator II is arranged below the lower catalyst layer. 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 technical scheme of the invention is as follows: the catalyst includes, but is not limited to, vanadium pentoxide.
The technical scheme of the invention is as follows: the pressure is gauge pressure.
The invention has the beneficial effects 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 invention adopts a method of filtering and dedusting the process gas which is cooled to 390-450 ℃ after being burned, does not produce a by-product of dust-containing dilute acid, and avoids secondary pollutants. The invention adopts the dust-removed SO-containing2The 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, compared with the prior art, the invention greatly shortens the process flow, obviously reduces the number of process equipment, correspondingly reduces the occupied area of production devices, does not need to use a large amount of circulating water and circulating acid, obviously reduces the energy consumption, reduces the operation cost, reduces the heat loss in the process flow, greatly improves the heat recovery rate and obviously increases the byproduct steam amount.
Drawings
FIG. 1 is a schematic diagram of a 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 invention is further illustrated by the following examples, without limiting the scope of the invention:
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 preheater 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 treatment device takes coke oven gas which is a byproduct of a coking device as fuel, the fuel is combusted in an incinerator 2 to generate high-temperature gas, the temperature of a hearth is controlled to be about 900 ℃ to 1200 ℃, 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 gas 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 blower 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, and the part of air is sent into the process gas-air preheater 3-2, heated to 460 ℃ by the process gas with higher temperature 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 (10)
1. A method for preparing sulfuric acid from coking desulfurization waste liquid is characterized by comprising the following steps: the method comprises the following steps:
(1) injecting gas or liquid fuel into the incinerator (2) for combustion to generate high-temperature gas, then injecting 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 gas with the temperature of 900-1200 ℃ in the incinerator (2)2，CO2，N2，O2，H2O high temperature process gas;
(2) the high-temperature process gas discharged from the incinerator (2) passes through a heat recovery system heat exchanger, steam is generated or other media are heated by using the heat of the process gas, 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 (4) for direct filtration and dust removal, and the temperature of the process gas after dust removal is still maintained above the temperature required by catalytic oxidation;
(4) the dedusted process gas enters a reactor (5), and SO in the process gas is obtained under the action of a catalyst2Further oxidized to SO3And has a part of SO3The reaction with water vapor generates sulfuric acid vapor, the oxidation reaction and the reaction for generating sulfuric acid are both exothermic reactions, a heat recovery system heat exchanger is arranged in the reactor (5) to recover reaction heat to generate vapor or heat other media, and the temperature of process gas discharged from the reactor (5) is controlled to be 290 +/-20 ℃;
(5) the process gas leaving the reactor (5) enters a sulfuric acid steam condenser (6), 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 (6) still contains a very small amount of SO2And then enters a tail gas treatment system, and is discharged after reaching the standard after being treated.
2. The method of claim 1, wherein: in the step (5), air is pressurized by an air fan (7) and then is sent into a sulfuric acid steam condenser (6) to cool process gas, the temperature of the air is increased after heat exchange, hot air at the outlet of the sulfuric acid steam condenser (6) is divided into two parts, wherein one part of the hot air is used as combustion-supporting air of an incinerator (2), the part of air is sent into a process gas-air preheater (3-2) of a heat recovery system, the part of combustion-supporting air is heated by the process gas with higher temperature, the temperature is increased again and then is sent into the incinerator (2), and the consumption of fuel of the incinerator is reduced; the rest air is sent into a feed water heater (3-3) 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.
3. The method according to claim 1 or 2, characterized in that: the heat exchanger of the heat recovery system consists of an evaporator I (3-1) arranged at the outlet of the incinerator (2), a process gas-air preheater (3-2), a steam superheater (3-5) and an evaporator II (3-6) arranged in the reactor (5), a water supply heater (3-3), a steam drum (3-4) and steam-water pipelines connected with the devices, the heat in the acid making process is recovered, steam is generated, the heat recovery system also adopts heat conduction oil or molten salt as a heat conduction medium, and the recovered heat can also produce steam or heat other process materials.
4. The method of claim 3, wherein: the method comprises the following steps that externally fed feed water is preheated to 180 +/-50 ℃ by hot air through a feed water heater (3-3), the feed water is fed into a steam drum (3-4) to be mixed with furnace water, the furnace water in the steam drum (3-4) flows into an evaporator I (3-1) at an outlet of an incinerator and an evaporator II (3-6) arranged in a reactor respectively, the heated part of the furnace water in the evaporator I (3-1) and the evaporator II (3-6) is evaporated to generate a steam-water mixture, the steam-water mixture flows back to the steam drum (3-4) under the action of thermosiphon, steam and the furnace water are separated in the steam drum (3-4), the furnace water continuously enters the evaporator I (3-1) and the evaporator II (3-6) to circulate, and medium-pressure saturated steam is separated out of the steam drum; the saturated steam is sent into the reactor again and is provided with a steam superheater (3-5), and the saturated steam is heated by the process gas and is externally supplied as medium-pressure superheated steam.
5. The method of claim 1, wherein: the water content of the desulfurization waste liquid is more than 40 percent.
6. The method of claim 1, wherein: the system for preparing sulfuric acid from coking desulfurization waste liquid 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).
7. The method of claim 3, 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 preheater (3-2), a water supply output pipeline is connected with a steam drum (3-4) after passing through the 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).
8. The method of claim 6, 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).
9. The method of claim 6, 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.
10. The method of claim 9, 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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