CN111071995A - Method for preparing industrial sulfuric acid by using sulfur-containing waste liquid - Google Patents
Method for preparing industrial sulfuric acid by using sulfur-containing waste liquid Download PDFInfo
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- CN111071995A CN111071995A CN201911331376.XA CN201911331376A CN111071995A CN 111071995 A CN111071995 A CN 111071995A CN 201911331376 A CN201911331376 A CN 201911331376A CN 111071995 A CN111071995 A CN 111071995A
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- sulfuric acid
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 110
- 239000011593 sulfur Substances 0.000 title claims abstract description 110
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000007788 liquid Substances 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 50
- 239000002002 slurry Substances 0.000 claims abstract description 48
- 238000001035 drying Methods 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 239000003546 flue gas Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- 239000000571 coke Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000006188 syrup Substances 0.000 claims description 10
- 235000020357 syrup Nutrition 0.000 claims description 10
- 238000004939 coking Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 5
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 230000009615 deamination Effects 0.000 claims description 5
- 238000006481 deamination reaction Methods 0.000 claims description 5
- 238000007791 dehumidification Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052743 krypton Inorganic materials 0.000 claims description 5
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052754 neon Inorganic materials 0.000 claims description 5
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 229910052704 radon Inorganic materials 0.000 claims description 5
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002918 waste heat Substances 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- 230000023556 desulfurization Effects 0.000 abstract description 7
- 230000004087 circulation Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000003034 coal gas Substances 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention provides a method for preparing industrial sulfuric acid by using sulfur-containing waste liquid, belonging to the field of industrial wastewater treatment, the method mixes the sulfur-containing waste liquid generated by ammonia process (HPF process) coal gas desulfurization, and a filter press is adopted to filter out elemental sulfur to obtain first sulfur slurry and filtered clear liquid; evaporating and concentrating the filtered desulfurization clear solution into second sulfur slurry, mixing the first sulfur slurry and the second sulfur slurry into thick slurry, and conveying the thick slurry to a drying working section; the drying section adopts a closed circulation drying mode which takes inert gas as a medium to process the concentrated sulfur slurry to obtain coarse sulfur powder. Feeding the crude sulfur into a sulfur burning furnace to be burnt into SO together with oxygen-enriched air2The invention mainly solves the environmental protection problem in the drying process and solves the tail gas ultralow emission problem through the energy-saving and emission-reducing measures of pretreatment and oxygen-enriched combustion and process control.
Description
Technical Field
The invention belongs to the field of industrial wastewater treatment, and particularly relates to a method for preparing industrial sulfuric acid by using sulfur-containing waste liquid.
Background
The desulfurization waste liquid and sulfur foam produced by desulfurization by HPF and PDS methods in a coking plant are a better production process technology for solving the environmental protection problem of the desulfurization waste liquid. In the production process of preparing sulfuric acid by a dry method, desulfurization waste liquid and sulfur foam are processed into solid crude sulfur in a drying mode and then are combusted to prepare sulfuric acid. The production process has the secondary environmental protection problem of the drying process, which is mainly represented by the problems of dust and smell of the field environment, safety in the drying process, tail gas emission and the like, energy-saving measures need to be optimized, and the tail gas emission is ultralow. Until now, there has been no document describing how to prevent secondary pollution in the drying process. The problems influence the environmental protection control and project investment income of the acid preparation from the desulfurization waste liquid, and must be solved to ensure the advancement and normal long-term operation of the acid preparation process.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing industrial sulfuric acid by using sulfur-containing waste liquid, which can avoid the adverse factors, realize the stable operation of a device and ensure the environmental protection and economic benefits.
The content of the invention is as follows: a method for preparing industrial sulfuric acid by using sulfur-containing waste liquid is characterized by comprising the following steps: the method for preparing the industrial sulfuric acid by using the sulfur-containing waste liquid comprises the following steps:
s1, collecting sulfur-containing waste liquid, conveying the sulfur-containing waste liquid into a precise filtering and concentrating unit through a pipeline, and filtering by using a filter press to obtain first sulfur slurry containing elemental sulfur and filtered clear liquid, wherein the elemental sulfur is intercepted, and the moisture content of sulfur paste is controlled to be below 35%;
s2, introducing the filtered clear liquid obtained in the step S1 into an evaporation concentration unit, and concentrating the filtered clear liquid into second syrup by adopting a multi-effect evaporator, wherein the water content of the second syrup is controlled to be 50-55%;
s3, mixing the first sulfur slurry obtained in the step S1 and the second sulfur slurry obtained in the step S2 to form thick slurry, feeding the thick slurry into a drying unit through a pipeline, taking inert gas as a drying medium, drying the thick slurry in a closed cycle manner to prepare coarse sulfur fine powder particles;
s4, feeding the coarse sulfur fine powder particles prepared in the step S3 into a sulfur burning unit, adding coke oven gas, introducing oxygen-enriched air for burning to generate sulfur dioxide flue gas, cooling the sulfur dioxide flue gas from the sulfur burning furnace by a waste heat boiler, recovering steam, feeding the flue gas subjected to cooling treatment into a purification unit for impurity removal and dehumidification, and dehydrating by a drying tower to obtain sulfur dioxide gas;
s5, enabling the sulfur dioxide gas obtained in the step S4 to pass through a conversion unit, preparing an industrial sulfuric acid finished product containing 93-98% of sulfuric acid by adopting a two-rotation and two-absorption method, returning the prepared industrial sulfuric acid finished product to a deamination system of a coking plant to remove ammonia in coke oven gas to prepare an ammonium sulfate product, and absorbing tail gas by the tail gas to ensure that the tail gas is discharged in an ultralow manner.
Preferably, the sulfur-containing waste liquid in step S1 contains 5 to 12 wt% of sulfur and 12 to 30 wt% of salt, based on the weight fraction.
Preferably, the salt is mainly at least one of sulfur, ammonium thiocyanate, ammonium thiosulfate and ammonium sulfate.
Preferably, the first sulfur slurry in the step S1 has a solid content of 60-70 wt% in terms of weight fraction, and the total amount of suspended matter in the filtered clear solution is 0-20 ppm.
Preferably, the second slurry in step S2 has a solid content of 45-50 wt% in terms of weight fraction.
Preferably, the inert gas is one of nitrogen, water vapor, carbon dioxide, helium, neon, argon, krypton, xenon and radon.
Preferably, the water content of the coarse sulfur fine powder particles in the step S3 is 2-4 wt%.
Preferably, the oxygen volume percentage of the oxygen-enriched air in the step S4 is 30-40%, and the volume percentage of the sulfur dioxide contained in the sulfur dioxide flue gas is 7-15%.
Preferably, the conversion device in the step S5 is a 3+2 five-stage twice conversion device.
The 3+ 2-stage twice conversion device comprises a converter, a first heat exchanger, a second heat exchanger, a third heat exchanger, a fourth heat exchanger and a fifth heat exchanger, wherein the converter, the first heat exchanger, the second heat exchanger, the third heat exchanger, the fourth heat exchanger and the fifth heat exchanger, the first absorption tower and the second absorption tower are communicated with the converter, the first heat exchanger, the second heat exchanger, the fourth heat exchanger and the fifth heat exchanger in sequence according to the flowing order of furnace gas dried by the drying tower; the furnace gas dried by the drying tower is sequentially sent to a third heat exchanger and a first heat exchanger through a sulfur dioxide fan for heat exchange and then enters a first section of a converter, the furnace gas after first section conversion enters the first heat exchanger for heat exchange and then enters a second section of the converter, the furnace gas after second section conversion enters a second heat exchanger for heat exchange and then enters a third section of the converter, the furnace gas after third section conversion enters a third heat exchanger for heat exchange and then enters a first absorption tower for primary absorption, the furnace gas after primary absorption enters a fourth section of the converter after sequentially passing through a fifth heat exchanger, a fourth heat exchanger and a second heat exchanger for heat exchange and then enters a fifth section of the converter, and the furnace gas after fifth section conversion enters a fifth heat exchanger for heat exchange and then enters a second absorption tower for secondary absorption.
Wherein, the two-absorption in the two-conversion two-absorption method is a dry absorption process, the dry absorption process adopts a three-tower three-groove process, an acid circulation absorption system adopts two acid circulations, a drying tower adopts 93 wt% of H2SO4 circulation, and an absorption tower and a second absorption tower adopt 98 wt% of H2SO4And circulating, and designing a sulfuric acid product switching device with two concentrations of 93% and 98%. The circulating acid cooling system consists of two absorption tower acid coolers and one drying tower acid cooler. The acid cooling circulation system is basically set as follows: tank → pump → acid cooler → tower → tank.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the method for preparing the industrial sulfuric acid by using the sulfur-containing waste liquid, the drying mode adopts the closed circulating inert gas medium, the device arrangement is compact, the occupied area is small, no dust and odor are generated on the site, no tail gas is discharged, and the condensate is recycled. Different from the traditional drying process, the inert gas is used as a drying medium, so that secondary pollution caused by waste gas generated in the drying process can be prevented, and the acid making efficiency is improved.
2. According to the method for preparing the industrial sulfuric acid by using the sulfur-containing waste liquid, mature and efficient filter pressing equipment and a multi-effect evaporator are adopted in the pretreatment process, the moisture of the concentrated slurry entering the system is reduced (by 5-10%), and the drying energy consumption is reduced (by 20-40 ten thousand yuan per year).
3. According to the method for preparing the industrial sulfuric acid by using the sulfur-containing waste liquid, the oxygen-enriched combustion technology is adopted, the air introduction amount is reduced, the concentration of sulfur dioxide in furnace gas is improved and can reach 8-10%, the device investment is reduced, the energy-saving effect of water, electricity and gas is realized, and the energy-saving benefit of 50-100 ten thousand yuan/year is preliminarily estimated; the nitrogen introduction amount is reduced, the combustion temperature and the oxygen enrichment amount are reasonably controlled, the generation amount of nitrogen oxides is reduced, and the cost of subsequent treatment is reduced.
4. The method for preparing the industrial sulfuric acid by using the sulfur-containing waste liquid adopts an imported catalyst, improves the conversion rate, and is provided with a denitration device and a tail gas absorption device, and the measures enable the tail gas emission to reach the ultralow standard.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Example 1
A method for preparing industrial sulfuric acid by using sulfur-containing waste liquid comprises the following steps:
s1, collecting sulfur-containing waste liquid, conveying the sulfur-containing waste liquid into a precise filtering and concentrating unit through a pipeline, and filtering by using a filter press to obtain first sulfur slurry containing elemental sulfur and filtered clear liquid, wherein the elemental sulfur is intercepted, and the moisture content of sulfur paste is controlled to be below 35%;
s2, introducing the filtered clear liquid obtained in the step S1 into an evaporation concentration unit, and concentrating the filtered clear liquid into second syrup by using a multi-effect evaporator, wherein the water content of the second syrup is controlled to be 50%;
s3, mixing the first sulfur slurry obtained in the step S1 and the second sulfur slurry obtained in the step S2 to form thick slurry, feeding the thick slurry into a drying unit through a pipeline, taking inert gas as a drying medium, drying the thick slurry in a closed cycle manner to prepare coarse sulfur fine powder particles;
s4, feeding the coarse sulfur fine powder particles prepared in the step S3 into a sulfur burning unit, adding coke oven gas, introducing oxygen-enriched air for burning to generate sulfur dioxide flue gas, cooling the sulfur dioxide flue gas from the sulfur burning furnace by a waste heat boiler, recovering steam, feeding the flue gas subjected to cooling treatment into a purification unit for impurity removal and dehumidification, and dehydrating by a drying tower to obtain sulfur dioxide gas;
s5, enabling the sulfur dioxide gas obtained in the step S4 to pass through a conversion unit, preparing an industrial sulfuric acid finished product containing 93-98% of sulfuric acid by adopting a two-rotation and two-absorption method, returning the prepared industrial sulfuric acid finished product to a deamination system of a coking plant to remove ammonia in coke oven gas to prepare an ammonium sulfate product, and absorbing tail gas by the tail gas to ensure that the tail gas is discharged in an ultralow manner.
Preferably, the sulfur-containing waste liquid in step S1 contains 5 wt% of sulfur and 12 wt% of salt, based on weight fraction.
Preferably, the salt is mainly at least one of sulfur, ammonium thiocyanate, ammonium thiosulfate and ammonium sulfate.
Preferably, the first sulfur slurry in step S1 has a solid content of 60 wt% and the total amount of suspended matter in the filtered clear solution is 10 ppm.
Preferably, the second slurry in step S2 has a solid content of 45 wt% in terms of weight fraction.
Preferably, the inert gas is one of nitrogen, water vapor, carbon dioxide, helium, neon, argon, krypton, xenon and radon.
Preferably, the water content of the coarse sulfur fine powder particles in the step S3 is 2 wt%.
Preferably, the oxygen content of the oxygen-enriched air in the step S4 is 30 vol%, and the sulfur dioxide content in the sulfur dioxide flue gas is 7 vol%.
Preferably, the conversion device in the step S5 is a 3+2 five-stage twice conversion device.
Example 2
A method for preparing industrial sulfuric acid by using sulfur-containing waste liquid comprises the following steps:
s1, collecting sulfur-containing waste liquid, conveying the sulfur-containing waste liquid into a precise filtering and concentrating unit through a pipeline, and filtering by using a filter press to obtain first sulfur slurry containing elemental sulfur and filtered clear liquid, wherein the elemental sulfur is intercepted, and the moisture content of sulfur paste is controlled to be below 35%;
s2, introducing the filtered clear liquid obtained in the step S1 into an evaporation concentration unit, and concentrating the filtered clear liquid into second syrup by using a multi-effect evaporator, wherein the water content of the second syrup is controlled to be 55%;
s3, mixing the first sulfur slurry obtained in the step S1 and the second sulfur slurry obtained in the step S2 to form thick slurry, feeding the thick slurry into a drying unit through a pipeline, taking inert gas as a drying medium, drying the thick slurry in a closed cycle manner to prepare coarse sulfur fine powder particles;
s4, feeding the coarse sulfur fine powder particles prepared in the step S3 into a sulfur burning unit, adding coke oven gas, introducing oxygen-enriched air for burning to generate sulfur dioxide flue gas, cooling the sulfur dioxide flue gas from the sulfur burning furnace by a waste heat boiler, recovering steam, feeding the flue gas subjected to cooling treatment into a purification unit for impurity removal and dehumidification, and dehydrating by a drying tower to obtain sulfur dioxide gas;
s5, enabling the sulfur dioxide gas obtained in the step S4 to pass through a conversion unit, preparing an industrial sulfuric acid finished product containing 93-98% of sulfuric acid by adopting a two-rotation and two-absorption method, returning the prepared industrial sulfuric acid finished product to a deamination system of a coking plant to remove ammonia in coke oven gas to prepare an ammonium sulfate product, and absorbing tail gas by the tail gas to ensure that the tail gas is discharged in an ultralow manner.
Preferably, the sulfur-containing waste liquid in step S1 contains 12 wt% of sulfur and 30 wt% of salt, based on weight fraction.
Preferably, the salt is mainly at least one of sulfur, ammonium thiocyanate, ammonium thiosulfate and ammonium sulfate.
Preferably, the first sulfur slurry in step S1 has a solid content of 70 wt% and the total amount of suspended matter in the filtered clear solution is 20 ppm.
Preferably, the second slurry in step S2 has a solid content of 50 wt% based on the weight fraction.
Preferably, the inert gas is one of nitrogen, water vapor, carbon dioxide, helium, neon, argon, krypton, xenon and radon.
Preferably, the moisture content of the coarse sulfur fine powder particles in step S3 is 4 wt%.
Preferably, the oxygen content of the oxygen-enriched air in the step S4 is 40% by volume, and the sulfur dioxide flue gas contains 15% by volume of sulfur dioxide.
Preferably, the conversion device in the step S5 is a 3+2 five-stage twice conversion device.
Example 3
A method for preparing industrial sulfuric acid by using sulfur-containing waste liquid comprises the following steps:
s1, collecting sulfur-containing waste liquid, conveying the sulfur-containing waste liquid into a precise filtering and concentrating unit through a pipeline, and filtering by using a filter press to obtain first sulfur slurry containing elemental sulfur and filtered clear liquid, wherein the elemental sulfur is intercepted, and the moisture content of sulfur paste is controlled to be below 35%;
s2, introducing the filtered clear liquid obtained in the step S1 into an evaporation concentration unit, and concentrating the filtered clear liquid into second syrup by using a multi-effect evaporator, wherein the water content of the second syrup is controlled to be 52%;
s3, mixing the first sulfur slurry obtained in the step S1 and the second sulfur slurry obtained in the step S2 to form thick slurry, feeding the thick slurry into a drying unit through a pipeline, taking inert gas as a drying medium, drying the thick slurry in a closed cycle manner to prepare coarse sulfur fine powder particles;
s4, feeding the coarse sulfur fine powder particles prepared in the step S3 into a sulfur burning unit, adding coke oven gas, introducing oxygen-enriched air for burning to generate sulfur dioxide flue gas, cooling the sulfur dioxide flue gas from the sulfur burning furnace by a waste heat boiler, recovering steam, feeding the flue gas subjected to cooling treatment into a purification unit for impurity removal and dehumidification, and dehydrating by a drying tower to obtain sulfur dioxide gas;
s5, enabling the sulfur dioxide gas obtained in the step S4 to pass through a conversion unit, preparing an industrial sulfuric acid finished product containing 93-98% of sulfuric acid by adopting a two-rotation and two-absorption method, returning the prepared industrial sulfuric acid finished product to a deamination system of a coking plant to remove ammonia in coke oven gas to prepare an ammonium sulfate product, and absorbing tail gas by the tail gas to ensure that the tail gas is discharged in an ultralow manner.
Preferably, the sulfur-containing waste liquid in step S1 contains 8 wt% of sulfur and 20 wt% of salt, in terms of weight fraction.
Preferably, the salt is mainly at least one of sulfur, ammonium thiocyanate, ammonium thiosulfate and ammonium sulfate.
Preferably, the first sulfur slurry in step S1 has a solid content of 65 wt% and the total amount of suspended matter in the filtered supernatant is 15 ppm.
Preferably, the second slurry in step S2 has a solid content of 48 wt% based on the weight fraction.
Preferably, the inert gas is one of nitrogen, water vapor, carbon dioxide, helium, neon, argon, krypton, xenon and radon.
Preferably, the water content of the coarse sulfur fine powder particles in the step S3 is 3 wt%.
Preferably, the oxygen percentage of the oxygen-enriched air in the step S4 is 35% by volume, and the sulfur dioxide flue gas contains 12% by volume of sulfur dioxide.
Preferably, the conversion device in the step S5 is a 3+2 five-stage twice conversion device.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A method for preparing industrial sulfuric acid by using sulfur-containing waste liquid is characterized by comprising the following steps: the method for preparing the industrial sulfuric acid by using the sulfur-containing waste liquid comprises the following steps:
s1, collecting sulfur-containing waste liquid, conveying the sulfur-containing waste liquid into a precise filtering and concentrating unit through a pipeline, and filtering by using a filter press to obtain first sulfur slurry containing elemental sulfur and filtered clear liquid, wherein the elemental sulfur is intercepted, and the moisture content of sulfur paste is controlled to be below 35%;
s2, introducing the filtered clear liquid obtained in the step S1 into an evaporation concentration unit, and concentrating the filtered clear liquid into second syrup by adopting a multi-effect evaporator, wherein the water content of the second syrup is controlled to be 50-55%;
s3, mixing the first sulfur slurry obtained in the step S1 and the second sulfur slurry obtained in the step S2 to form thick slurry, feeding the thick slurry into a drying unit through a pipeline, taking inert gas as a drying medium, drying the thick slurry in a closed cycle manner to prepare coarse sulfur fine powder particles;
s4, feeding the coarse sulfur fine powder particles prepared in the step S3 into a sulfur burning unit, adding coke oven gas, introducing oxygen-enriched air for burning to generate sulfur dioxide flue gas, cooling the sulfur dioxide flue gas from the sulfur burning furnace by a waste heat boiler, recovering steam, feeding the flue gas subjected to cooling treatment into a purification unit for impurity removal and dehumidification, and dehydrating by a drying tower to obtain sulfur dioxide gas;
s5, enabling the sulfur dioxide gas obtained in the step S4 to pass through a conversion unit, preparing an industrial sulfuric acid finished product containing 93-98% of sulfuric acid by adopting a two-rotation and two-absorption method, returning the prepared industrial sulfuric acid finished product to a deamination system of a coking plant to remove ammonia in coke oven gas to prepare an ammonium sulfate product, and absorbing tail gas by the tail gas to ensure that the tail gas is discharged in an ultralow manner.
2. The method for preparing industrial sulfuric acid from sulfur-containing waste liquid according to claim 1, characterized in that: in the step S1, the sulfur-containing waste liquid contains, by weight, 5 to 12 wt% of sulfur and 12 to 30 wt% of salt.
3. The method for preparing industrial sulfuric acid from sulfur-containing waste liquid according to claim 2, characterized in that: the salt is mainly at least one of sulfur, ammonium thiocyanate, ammonium thiosulfate and ammonium sulfate.
4. The method for preparing industrial sulfuric acid from sulfur-containing waste liquid according to claim 1, characterized in that: the first sulfur slurry in the step S1 has a solid content of 60-70 wt% and a total amount of suspended matter in the filtered clear solution of 0-20 ppm.
5. The method for preparing industrial sulfuric acid from sulfur-containing waste liquid according to claim 1, characterized in that: the second slurry in the step S2 contains 45-50 wt% of solid content.
6. The method for preparing industrial sulfuric acid from sulfur-containing waste liquid according to claim 1, characterized in that: the inert gas is one of nitrogen, water vapor, carbon dioxide, helium, neon, argon, krypton, xenon and radon.
7. The method for preparing industrial sulfuric acid from sulfur-containing waste liquid according to claim 1, characterized in that: the water content of the coarse sulfur fine powder particles in the step S3 is 2-4 wt%.
8. The method for preparing industrial sulfuric acid from sulfur-containing waste liquid according to claim 1, characterized in that: in the step S4, the oxygen volume percentage of the oxygen-enriched air is 30-40%, and the volume percentage of sulfur dioxide contained in the sulfur dioxide flue gas is 7-15%.
9. The method for preparing industrial sulfuric acid from sulfur-containing waste liquid according to claim 1, characterized in that: the conversion device in the step S5 is a 3+2 five-stage twice conversion device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911331376.XA CN111071995A (en) | 2019-12-21 | 2019-12-21 | Method for preparing industrial sulfuric acid by using sulfur-containing waste liquid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807332A (en) * | 2020-07-09 | 2020-10-23 | 山东绿知源环保工程有限公司 | High-efficiency method and device for preparing sulfuric acid from coking plant desulfurization waste liquid |
| CN112093779A (en) * | 2020-09-18 | 2020-12-18 | 南京合工智能环保研究院有限公司 | Acid preparation system and acid preparation process |
| CN113912022A (en) * | 2020-07-10 | 2022-01-11 | 宝武炭材料科技有限公司 | SO in process gas at outlet of combustion furnace of sulfuric acid lifting device2Concentration process |
| CN114956421A (en) * | 2022-03-25 | 2022-08-30 | 同兴环保科技股份有限公司 | Zero-emission method for preparing acid from desulfurization waste liquid and sulfur foam |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795604A (en) * | 2012-09-11 | 2012-11-28 | 宜宾海翔化工有限责任公司 | System for treating sulfur residue |
| CN103552992A (en) * | 2013-10-30 | 2014-02-05 | 中石化南京工程有限公司 | System and method for preparing acid by using sulfur-containing wastewater through dry method |
| CA2995559A1 (en) * | 2015-09-04 | 2017-03-09 | Thyssenkrupp Industrial Solutions Ag | Method and device for producing sulfuric acid |
| CN109384200A (en) * | 2018-12-27 | 2019-02-26 | 中冶焦耐(大连)工程技术有限公司 | Process and device for treating waste liquid of low-purity sulfur and secondary salt produced by coke oven gas desulfurization |
| CN109607682A (en) * | 2018-11-29 | 2019-04-12 | 山东莱钢节能环保工程有限公司 | A kind of comprehensive reutilization method of novel coke-oven plant HPF method coal gas desulfurization waste liquid |
-
2019
- 2019-12-21 CN CN201911331376.XA patent/CN111071995A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795604A (en) * | 2012-09-11 | 2012-11-28 | 宜宾海翔化工有限责任公司 | System for treating sulfur residue |
| CN103552992A (en) * | 2013-10-30 | 2014-02-05 | 中石化南京工程有限公司 | System and method for preparing acid by using sulfur-containing wastewater through dry method |
| CA2995559A1 (en) * | 2015-09-04 | 2017-03-09 | Thyssenkrupp Industrial Solutions Ag | Method and device for producing sulfuric acid |
| CN109607682A (en) * | 2018-11-29 | 2019-04-12 | 山东莱钢节能环保工程有限公司 | A kind of comprehensive reutilization method of novel coke-oven plant HPF method coal gas desulfurization waste liquid |
| CN109384200A (en) * | 2018-12-27 | 2019-02-26 | 中冶焦耐(大连)工程技术有限公司 | Process and device for treating waste liquid of low-purity sulfur and secondary salt produced by coke oven gas desulfurization |
Non-Patent Citations (2)
| Title |
|---|
| 程亮等: "液体二氧化硫技改工程的探索实践", 《甘肃冶金》 * |
| 黄英: "《化工过程节能与优化设计》", 28 February 2018, 西北工业大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807332A (en) * | 2020-07-09 | 2020-10-23 | 山东绿知源环保工程有限公司 | High-efficiency method and device for preparing sulfuric acid from coking plant desulfurization waste liquid |
| CN113912022A (en) * | 2020-07-10 | 2022-01-11 | 宝武炭材料科技有限公司 | SO in process gas at outlet of combustion furnace of sulfuric acid lifting device2Concentration process |
| CN112093779A (en) * | 2020-09-18 | 2020-12-18 | 南京合工智能环保研究院有限公司 | Acid preparation system and acid preparation process |
| CN114956421A (en) * | 2022-03-25 | 2022-08-30 | 同兴环保科技股份有限公司 | Zero-emission method for preparing acid from desulfurization waste liquid and sulfur foam |
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