CN113357652A - Treatment method of desulfurization waste liquid and sulfur foam - Google Patents
Treatment method of desulfurization waste liquid and sulfur foam Download PDFInfo
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- CN113357652A CN113357652A CN202110733771.1A CN202110733771A CN113357652A CN 113357652 A CN113357652 A CN 113357652A CN 202110733771 A CN202110733771 A CN 202110733771A CN 113357652 A CN113357652 A CN 113357652A
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- waste liquid
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- 239000007788 liquid Substances 0.000 title claims abstract description 82
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 70
- 239000011593 sulfur Substances 0.000 title claims abstract description 70
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 68
- 230000023556 desulfurization Effects 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 56
- 239000006260 foam Substances 0.000 title claims abstract description 43
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 claims abstract description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 19
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 17
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 238000002485 combustion reaction Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 239000003034 coal gas Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
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- 239000007921 spray Substances 0.000 claims abstract description 4
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- 239000007789 gas Substances 0.000 claims description 50
- 239000002253 acid Substances 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
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- 238000000746 purification Methods 0.000 claims description 23
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- 239000012535 impurity Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims description 3
- 238000007791 dehumidification Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
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- 230000000694 effects Effects 0.000 description 8
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
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- 230000003137 locomotive effect Effects 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- 229910000885 Dual-phase steel Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 230000009291 secondary effect Effects 0.000 description 1
- 230000003584 silencer Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 230000009293 tertiary effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
- F23G5/46—Recuperation of heat
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2206/00—Waste heat recuperation
- F23G2206/20—Waste heat recuperation using the heat in association with another installation
- F23G2206/203—Waste heat recuperation using the heat in association with another installation with a power/heat generating installation
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/12—Heat utilisation in combustion or incineration of waste
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for treating desulfurization waste liquid and sulfur foam, and relates to the technical field of waste liquid treatment. The invention comprises four stages of incineration of desulfurization waste liquid and sulfur foam, catalytic oxidation of sulfur dioxide, absorption of sulfur trioxide and absorption of ammonia, and the treatment method of desulfurization waste liquid and sulfur foam comprises the following steps: step 1: feeding the desulfurization waste liquid and sulfur foam generated by ammonia-process coal gas desulfurization into a high-efficiency separation device to separate solid sulfur paste with the water content of less than or equal to 30%, and feeding the sulfur paste into an incinerator by using a screw machine; step 2: evaporating and concentrating the separated clear liquid to obtain concentrated slurry with concentration of 50-60%, pumping to spray gun, and directly spraying into fluidized bed furnace for combustion with sulfur paste. The desulfurization waste liquid and the sulfur foam are heated at high temperatureTotal decomposition into N2、SO2、CO2、H2O, etc., SO formed2The gas is used for absorbing ammonia in the coal gas to produce ammonium sulfate after being converted and absorbed, no secondary pollution gas is discharged, and the environmental pollution of the desulfurization waste liquid and the sulfur foam is thoroughly solved.
Description
Technical Field
The invention relates to the technical field of waste liquid treatment, in particular to a method for treating desulfurization waste liquid and sulfur foam.
Background
Steelmaking is one of the largest energy production industries, the most used fuel in the steelmaking industry is coke, and the production of the coke also influences the economic benefit of the steelmaking industry, in the former production, coke oven gas generated by coking is directly used as fuel, and as the environmental protection consciousness of the country and even the world is improved, the current production system flow is slowly formed in order to further improve the industry profits; but also causes more serious environmental pollution problem, under such environment, the optimization and application of the desulfurization process are significant, various environmental protection processes have appeared in the modern market, in recent years, due to the rapid industrial development, serious air pollution and acid rain are formed in certain areas in China, because in the production work, a great amount of harmful smoke and harmful gas, such as sulfur dioxide and various nitrogen compounds, are discharged in the industries such as coal burning and the like, so that a desulfurization device is required to be used for removing the pollutants as much as possible, the environmental problem is faced, if effective measures are not taken in time, the environmental problem is further worsened, the self health of people is finally influenced, in recent years, the environmental protection pressure is further improved, and more strict requirements on the emission standard of harmful substances in the atmosphere are provided, the main emission is sulfur, hydrogen sulfide exists in the coke oven gas in a main form, the hydrogen sulfide is toxic and corrosive to equipment and pipelines, and when the gas is burnt as fuel, the hydrogen sulfide reacts with oxygen in the air to generate sulfur dioxide, so that air pollution is caused, and the coke oven gas purification and optimization process work is not slow;
at present, the coking industry commonly adopts an ammonia wet oxidation desulfurization process which takes HPF, PDS and the like as catalysts to remove H2S in coke oven gas and an HCN ammonia wet oxidation desulfurization dehydrogenation process to generate desulfurization waste liquid such as ammonium hydrogen sulfate, ammonium thiosulfate and the like and sulfur foam, so that how to improve the coking desulfurization effect, reduce the content of hydrogen sulfide in the gas and reduce the sulfur emission is always a difficult problem of environmental protection puzzling coking enterprises; therefore, a method for treating desulfurization waste liquid and sulfur foam is provided.
Disclosure of Invention
The present invention is directed to a method for treating a desulfurization waste liquid and sulfur foams, which solves the problems set forth in the background above.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a method for treating desulfurization waste liquid and sulfur foam, which comprises four stages of incineration of the desulfurization waste liquid and the sulfur foam, catalytic oxidation of sulfur dioxide, absorption of sulfur trioxide and absorption of ammonia, and comprises the following steps:
step 1: feeding the desulfurization waste liquid and sulfur foam generated by ammonia-process coal gas desulfurization into a high-efficiency separation device to separate solid sulfur paste with the water content of less than or equal to 30%, and feeding the sulfur paste into an incinerator by using a screw machine;
step 2: evaporating and concentrating the separated clear liquid to obtain concentrated slurry with concentration of 50-60%, pumping to spray gun, directly spraying into fluidized bed furnace, combusting with sulfur paste in different regions, and combusting with introduced hot air to obtain concentrated slurry containing 6-8% SO2The flue gas of (2);
step 3: based on the steps, after high-temperature dust removal, the waste heat is sent to a waste heat boiler to recover waste heat to generate medium-pressure saturated steam;
step 4: after the hot air heat exchanger and the cold air heat exchanger are used for heating the air entering the furnace, the air is sent to a purification process, and cooling, dehumidification and dehydration of a drying tower are carried out through the purification process;
step 5: based on the steps, preparing an industrial sulfuric acid product by a two-rotation and two-absorption (3+1) acid preparation process;
step 6: returning the industrial sulfuric acid to a desulfurization system of a coking plant to prepare ammonium sulfate;
step 7: and finishing the treatment of the desulfurization waste liquid and the sulfur foam.
Preferably, in Step1, the desulfurized waste liquid and the sulfur foam conveyed from the desulfurization device of the coke-oven plant are conveyed to a high-efficiency centrifugal device through a filter pump for solid-liquid separation, the moisture content of the separated solid sulfur paste is about 25%, the solid sulfur paste is conveyed to an acid making battery compartment by a transfer locomotive, and the solid sulfur paste is conveyed to an incinerator for combustion through a scraper conveyor and a double-helix (variable frequency) conveying device.
Preferably, the filtered clear liquid in Step2 automatically flows to a clear liquid tank of a desulfurization boundary area, is conveyed to a desulfurization waste liquid storage tank of an acid making boundary area by a clear liquid pump through an outer pipe network, is conveyed to a condensate water preheater by a desulfurization waste liquid feeding pump, is evaporated and concentrated by a triple-effect evaporator, the concentrated feed liquid is pumped into a single-effect evaporator through a pump to be continuously evaporated and concentrated, and the concentrated feed liquid enters a double-effect evaporator through pressure difference to be continuously evaporated and concentrated and is then conveyed to a concentrated slurry tank by a discharge pump.
Preferably, the high-temperature furnace gas discharged from the incinerator in Step3 is dedusted by the auxiliary combustion chamber, enters the medium-pressure waste heat boiler, the hot air preheater and the cold air preheater to recover heat, is cooled to about 300 ℃, and enters the purification process.
Preferably, the furnace gas purification in the Step4 purification process adopts a totally-enclosed pickling purification process of 'dynamic wave-packed tower-two-stage electric demister'.
Preferably, the '3 + 1' twice conversion process in Step5 uses imported high-quality catalyst, the conversion rate is controlled to be more than 99.85%, and the heat exchange processes of the conversion are IV, I-III and II.
Preferably, the dilute sulfuric acid solution in Step6 is sent to a regulator, the pH value is adjusted to about 7 by using a condensate evaporated in a pretreatment procedure, a 1-3% dilute ammonium sulfate solution is generated, impurities and iron-aluminum precipitates are removed by three-stage filtration through a precision filter, a security filter and ultrafiltration, clear liquid is sent to an LM membrane group for separation and concentration, the ammonium sulfate is concentrated to 15% -18% of concentration and sent to an ammonium sulfate device, clean water produced by the membrane group is internally digested by an acid making system, and the redundant part is sent to a desulfurization system to be used as make-up water.
The invention has the following beneficial effects:
the invention relates to a method for treating desulfurization waste liquid and sulfur foam, which decomposes desulfurization waste liquid and sulfur foam into N at high temperature2、SO2、CO2、H2O, etc., SO formed2The gas is used for absorbing ammonia in the coal gas to produce ammonium sulfate after being converted and absorbed, no secondary pollution gas is discharged, and the environmental pollution of the desulfurization waste liquid and the sulfur foam is thoroughly solved.
The invention also provides a method for treating the desulfurization waste liquid and the sulfur foam, wherein the desulfurization waste liquid and the sulfur foam sent from the coking desulfurization process are directly burnt in an incinerator without being continuously treated by sulfur paste separated by a high-efficiency centrifugal machine and desulfurization waste liquid thick slurry subjected to triple-effect evaporation concentration, so that the investment and the operating cost of the continuous treatment part are reduced.
The method for treating the desulfurization waste liquid and the sulfur foam has the advantages of simple operation process, low treatment cost, high treatment efficiency and strong popularization value.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a method for treating desulfurized waste liquid and sulfur foam according to the present invention;
FIG. 2 is a block flow diagram of a process for pretreating desulfurization waste liquid and sulfur foam according to the present invention;
FIG. 3 is a block flow diagram of an incineration process of desulfurized waste liquid and sulfur foam of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
please refer to fig. 1-3: the invention relates to a method for treating desulfurization waste liquid and sulfur foam, which comprises four stages of incineration of the desulfurization waste liquid and the sulfur foam, catalytic oxidation of sulfur dioxide, absorption of sulfur trioxide and absorption of ammonia, and comprises the following steps:
step 1: feeding the desulfurization waste liquid and sulfur foam generated by ammonia-process coal gas desulfurization into a high-efficiency separation device to separate solid sulfur paste with the water content of less than or equal to 30%, and feeding the sulfur paste into an incinerator by using a screw machine;
step 2: evaporating and concentrating the separated clear liquid to obtain concentrated slurry with concentration of 50-60%, pumping to spray gun, directly spraying into fluidized bed furnace, combusting with sulfur paste in different regions, and combusting with introduced hot air to obtain concentrated slurry containing 6-8% SO2The flue gas of (2);
step 3: based on the steps, after high-temperature dust removal, the waste heat is sent to a waste heat boiler to recover waste heat to generate medium-pressure saturated steam;
step 4: after the hot air heat exchanger and the cold air heat exchanger are used for heating the air entering the furnace, the air is sent to a purification process, and cooling, dehumidification and dehydration of a drying tower are carried out through the purification process;
step 5: based on the steps, preparing an industrial sulfuric acid product by a two-rotation and two-absorption (3+1) acid preparation process;
step 6: returning the industrial sulfuric acid to a desulfurization system of a coking plant to prepare ammonium sulfate;
step 7: and finishing the treatment of the desulfurization waste liquid and the sulfur foam.
The thick slurry and the sulfur paste from the pretreatment process are continuously and uniformly added into an incinerator for boiling combustion through a pump and a metering screw respectively. The combustion-supporting air is passed through air combustion-supporting fan (silencer is set at inlet), and the combustion-supporting air and furnace gas after the waste heat boiler is cooled are passed through dew point-preventing air preheater, cold air heat exchanger and hot air heat exchanger to make heat exchange, and fed into the incineration furnace by means of bottom portion and middle section of incineration furnace. The material and air are subjected to combustion reaction at 1050-1150 ℃ to generate high-temperature SO2Furnace gas.
The burning of the sulfur paste and the sulfur salt is a violent exothermic reaction, the moisture content is controlled, the air addition excess coefficient is adjusted, and the stable burning can be controlled within the temperature range of 1050-1150 ℃. The self heat system in the incinerator is balanced, and coke oven gas is not required to be added.
The high-temperature furnace gas discharged from the incinerator is dedusted by the auxiliary combustion chamber, enters the medium-pressure waste heat boiler, the hot air preheater and the cold air preheater to recover heat, is cooled to about 300 ℃, and enters the purification process.
The temperature and pressure of 4.2MPa medium-pressure saturated steam generated by the waste heat boiler are reduced to 0.6MPa, and the steam is measured by a flowmeter and sent into a steam outer pipe network. The 0.2MPa steam required by the device is supplied after the secondary temperature and pressure reduction of the 0.6MPa steam in the device, and the original steam used during the driving is supplied by an outer pipe network.
Qualified desalted water for the boiler from the outer pipe is sent to a desalted water tank in a boundary area, is sent to a deaerator by a desalted water pump, is deaerated by the deaerator, and is sent to a waste heat boiler by a boiler water feeding pump to produce steam. The low-pressure steam required by the deaerator is provided by an internal steam pipe network.
In Step1, the desulfurized waste liquid and sulfur foam delivered from a desulfurization device of a coking plant are delivered to a high-efficiency centrifugal device through a filter pump for solid-liquid separation, the moisture content of the separated solid sulfur paste is about 25 percent, the separated solid sulfur paste is delivered to an acid making battery compartment by a transfer locomotive, and the solid sulfur paste is delivered to an incinerator for combustion through a scraper conveyor and a double-helix (variable frequency regulation) delivery device.
The filtered clear liquid in Step2 automatically flows to a clear liquid tank of a desulfurization boundary area, is conveyed to a desulfurization waste liquid storage tank of an acid making boundary area by a clear liquid pump through an outer pipe network, is conveyed to a condensate water preheater by a desulfurization waste liquid feeding pump, is evaporated and concentrated by a three-effect evaporator, the concentrated feed liquid is pumped into a one-effect evaporator through a pump to continue evaporation and concentration, enters a two-effect evaporator through pressure difference to continue evaporation and concentration, and is conveyed to a concentrated slurry tank by a discharge pump.
Wherein, the high-temperature furnace gas discharged from the incinerator in Step3 is dedusted by the auxiliary combustion chamber, enters the medium-pressure waste heat boiler, the hot air preheater and the cold air preheater to recover heat, is cooled to about 300 ℃, and enters the purification process.
Wherein, the furnace gas purification of the purification process in Step4 adopts a totally-enclosed pickling purification process of 'dynamic wave-packed tower-two-stage electric demister', the dilute acid produced in the purification process is directly sent to an LM membrane method processing system matched with the purification process, the dilute acid is completely converted into ammonium sulfate concentrated solution and clean water and is converted into a product for recovery, and the system does not discharge the dilute acid any more.
Wherein, the '3 + 1' twice conversion process in Step5 uses imported high-quality catalyst, the conversion rate is controlled to be above 99.85%, and the heat exchange processes of the conversion are IV, I-III and II.
Wherein, dilute sulphuric acid solution in Step6 is sent into a regulator, the pH value is adjusted to about 7 by using the evaporation condensate of the pretreatment procedure, dilute ammonium sulfate solution with the concentration of 1-3% is generated, impurities and iron-aluminum precipitate are removed by three-stage filtration of a precision filter, a security filter and ultrafiltration, clear liquid is sent into an LM membrane group for separation and concentration, the ammonium sulfate is concentrated to the concentration of 15% -18%, the ammonium sulfate solution is sent into an ammonium sulfate device, clean water produced by the membrane group is internally digested by an acid making system, and the redundant part is sent into a desulfurization system to be used as make-up water.
SO after foam removal of foam remover of drying tower2And (3) boosting the pressure of the 7-8% furnace gas by a sulfur dioxide blower, exchanging heat by an IV heat exchanger and an I heat exchanger to 420 ℃, and entering a converter. The first conversion is respectively carried out by the first, second and third catalyst layer reactions and the heat exchange of the heat exchangers I, II and III, the conversion rate reaches more than 94 percent, the furnace gas after the heat exchange is cooled to 180 ℃, and then enters an absorption tower, and 98 percent acid is generated in the absorption tower. Absorb off SO3The gas is subjected to acid mist removal by a demister at the top of the tower, secondary conversion is carried out, the gas is subjected to heat exchange by a heat exchanger III and a heat exchanger II respectively and then enters a converter for secondary conversion in four sections, the total conversion rate reaches over 99.85 percent, and the temperature of secondary converted gas is reduced to 165 ℃ after heat exchange by a heat exchanger IV and then enters a second absorption tower to absorb SO3。
The furnace gas purification adopts a totally-enclosed pickling purification process of 'dynamic wave-packed tower-two-stage electric demister'.
And cooling the furnace gas at the outlet of the incinerator to 300 ℃ through a waste heat boiler and an air cooler, then feeding the furnace gas into a dynamic wave washer, washing the furnace gas with 1-5% dilute acid, cooling the furnace gas to 75 ℃, and then feeding the furnace gas into a filler cooling tower. The packed tower is washed and cooled by dilute acid with the temperature of 65 ℃ and the concentration of 1 percent, and the circulating dilute acid is cooled by circulating water. The furnace gas with the temperature of the cooling tower of the filler reduced to 32 ℃ enters a two-stage electric demister connected in series to remove acid mist and other impurities, and the acid mist content of the gas at the outlet is less than or equal to 0.005g/Nm3Sending the mixture into a dry absorption working section; movable partThe dilute sulfuric acid with the concentration of 1-5% at the lower part of the dynamic wave washer is pressurized by a dynamic wave circulating pump, most of the dilute sulfuric acid enters the upper part of the dynamic wave washer to be sprayed, the rest of the dilute sulfuric acid enters a by-product dilute acid degassing tower, and the dilute acid after desorption is sent to a dilute acid membrane treatment system.
The filler cooling tower is mainly used for cooling the washing furnace gas, and the heat and the excessive moisture in the gas are cooled by circulating water and then are removed out of the system; in order to prevent the high-temperature gas from burning out equipment caused by the liquid breaking of the dynamic wave washer, a clear water elevated tank is arranged; because the purification working section is operated under negative pressure, in order to prevent the gas pipeline and the equipment from being damaged by pumping, a safety water seal is arranged behind the electric demister; the produced dilute acid is sent into a dilute acid treatment process, and is subjected to comprehensive treatment and then is utilized in a grading manner.
Example two:
the desulfurization waste liquid and sulfur foam treatment process mainly comprises four stages of incineration of the desulfurization waste liquid and sulfur foam, catalytic oxidation of sulfur dioxide, absorption of sulfur trioxide and absorption of ammonia, and the main reaction is as follows:
first stage (incineration)
NH4SCN+3O2＝2H2O+N2+SO2+CO2
(NH4)2S2O3+2.5O2＝4H2O+N2+2SO2
(NH4)2SO4+O2＝4H2O+N2+SO2
(NH4)2CO3+1.5O2＝4H2O+N2+CO2
S+O2＝SO2
2NH3+1.5O2＝N2+3H2O
Second stage (conversion)
SO2+0.5O2＝SO3
Third stage (absorption)
SO3+H2O＝H2SO4
Stage four (Ammonia absorption)
H2SO4+2NH3＝(NH4)2SO4
In the scheme, saturated low-pressure steam (less than or equal to 0.2MPa, provided by a medium-pressure steam produced by a waste heat boiler through temperature reduction and pressure reduction and provided by a steam outer pipe network during starting) enters a first-effect heating chamber shell pass to exchange heat with raw materials, enters a condensate water preheater to preheat the raw materials after condensation, can realize the reutilization of condensate water waste heat, and returns to an acid-making deaerator after preheating is finished; the secondary steam generated by the primary-effect separation chamber is used as a heat source of the secondary-effect heating chamber, and enters the shell pass of the tertiary-effect heating chamber to utilize the waste heat after exchanging heat with the tube pass feed liquid and condensing; secondary steam generated by the two-effect separation chamber is used as a heat source of the three-effect heating chamber, exchanges heat with tube side feed liquid and is condensed, and then enters a condensation water tank; secondary steam generated by the triple-effect separation chamber enters an indirect condenser to exchange heat with circulating water on the shell side of the indirect condenser for condensation, condensed water enters a condensed water tank for collection, the condensed water is pumped to a dilute acid membrane method treatment process, the redundant part is sent to a desulfurization process of a coking plant for use, and non-condensable gas in the indirect condenser is discharged to a tail gas treatment process by a vacuum pump and then is intensively discharged;
in order to ensure the fluidity of the evaporated and concentrated desulfurization concentrated slurry and prevent salt crystallization from blocking a pipeline, a concentrated slurry tank and a conveying pipeline maintain the temperature of materials in a low-pressure steam jacket and heat tracing mode, and the produced steam condensate is sent to a condensate water preheater to recover heat and then returns to a deaerator; the equipment such as the desulfurization waste liquid storage tank, the clear liquid groove, the thick slurry storage tank, the scraper conveyor, the screw conveyor and the like is provided with an air escape negative pressure system, and air escape is recovered and then is intensively sent to a furnace gas purification system for treatment.
In the scheme, two high-efficiency centrifuges are arranged, one centrifuge is used for one centrifuge, so that the production continuity and the flow tightness of the sulfur paste are realized, and the moisture control of the sulfur paste is ensured. The sulfur paste enters the incinerator by adopting a screw conveyor and frequency conversion adjustment, so that the stability and the adjustability of feeding are ensured, and the combustion uniformity of the sulfur paste in the incinerator is facilitated;
removing water from the centrifugally separated clear desulfurized waste liquid by adopting triple-effect evaporation concentration equipment, controlling the evaporation temperature and inhibiting the decomposition of salt in the waste liquid; the evaporation effect is controlled, the higher concentration of the desulfurization waste liquid is ensured to enter the incinerator, and the self heat balance of the incinerator is realized. In order to ensure the long-period operation effect of the evaporation system, the equipment material is a dual-phase steel material with better high-temperature corrosion resistance. The triple-effect evaporator is selected, so that the treatment effect of the desulfurization waste liquid can be realized, the steam consumption can be saved, and the operation cost is reduced;
the incinerator selects a vertical double-chamber incinerator, compared with a horizontal or single-chamber vertical incinerator, the incinerator has the advantages of better combustion effect, more uniform temperature system, stronger material applicability, furnace gas and dust separation effect, increase of the ash removal period of a follow-up boiler and reduction of labor intensity.
A fire tube type waste heat boiler and an air preheater are arranged at the outlet of the incinerator, and waste heat is recovered for producing medium-pressure saturated steam at the temperature of 4.2MPa and 253 ℃ and heating air entering the incinerator;
adopts four-stage '3 + 1' twice conversion, heat exchange process of 'IV, I-III and II' and domestic high-quality catalyst to make total conversion rate be up to 99.7%, and SO in tail gas can be fed out2The content is less than 30mg/Nm3The pollution to the environment is reduced to the maximum extent;
the drying tower and the first absorption tower adopt 98.5 percent acid for drying, and the second absorption tower adopts 98 percent acid for absorption. The temperature of the circulating acid is increased, which is beneficial to improving the drying and demisting effects;
the design of the dry absorption tower adopts a low-order tower arrangement, acid enters the head part of a circulating groove, and when the tower bottom does not accumulate acid in normal operation and stops, a part of acid is accumulated at the tower bottom;
adopt novel high-efficient equipment, save the investment, include:
firstly, high-pressure atomized concentrated solution is adopted in the incinerator for incineration, and the volumetric heat intensity of the incinerator is high.
And secondly, the drying tower and the absorption tower adopt disc-shaped bottom structures. The dry absorption tower adopts the column type support, saves the civil engineering expense. The filler support of the dry absorption tower adopts XDS alloy material, and the filler adopts a porcelain step ring with larger specific surface area and void ratio. The top of the drying tower adopts two layers of drawer type wire mesh demisters, and the upper parts of the first absorption tower and the second absorption tower adopt high-efficiency fiber demisters.
Thirdly, the blower adopts a frequency conversion adjusting mode.
And fourthly, the shell-and-tube heat exchanger of the convergent-divergent tube is adopted, and the heat exchanger is characterized by simple structure, high heat transfer coefficient, lower pressure drop, small equipment volume and higher cost performance.
And the acid cooler adopts a plate-type acid cooler, so that the equipment has high heat transfer efficiency, long service life, convenient maintenance and small occupied area. The circulating acid pipeline of the dry absorption tower is a stainless steel pipeline with anode protection, and the acid discharge pipeline is also a stainless steel pipeline.
Sixthly, the waste heat boiler adopts a fire tube type waste heat boiler with a single smoke channel.
And the device adopts an advanced DCS distributed control system to monitor the process parameters of the whole process, and has the functions of flow chart dynamic image display, parameter display image, regulation display image, alarm image, trend record display, automatic report printing and the like, and the monitoring of the whole production process can be basically completed in a main control room.
The scheme has an energy-saving effect, and comprises the steps of selecting high-efficiency separation equipment for sulfur foam in a pretreatment process, reducing the moisture in the sulfur paste to be below 30%, and reducing the moisture entering a furnace from the source; and a triple-effect evaporator is selected for evaporating the desulfurization waste liquid, so that the evaporation efficiency is improved, and the steam consumption is reduced. Compared with a double-effect evaporator, the energy can be saved by more than 30 percent; the heat of the desulfurization waste liquid incineration system is self-balanced, external heat sources such as coke oven gas and the like do not need to be supplemented, the air addition amount is reduced, the furnace gas amount is reduced, the concentration of sulfur dioxide in the furnace gas is improved, the size of subsequent equipment is reduced, and the operation cost is reduced; the concentration of sulfur dioxide in the incinerator gas is controlled to be 7-8%, the acid making requirement is met, a conversion electric furnace is not needed to operate, oxygen-enriched combustion is not needed, and the electricity consumption cost is saved; the air blower, the sulfur dioxide fan and important operation equipment are all adjusted by the frequency converter, so that the operation electricity charge is saved, and the operation cost is reduced.
The scheme has the advantages of in-place environmental protection measures, no secondary pollution and good field environment, and comprises the steps of preparing acid by adopting imported high-quality catalyst and SO2The conversion rate is more than 99.85 percent, the tail gas is provided with a washing system and an electric demisting system, and the SO of the tail gas is controlled2≤30mg/Nm3Coking desulfurizationThe denitration treatment system carries out centralized treatment, so that more sulfuric acid products are produced, the treatment load of the denitration and desulfurization system is reduced, and the direct treatment cost and the environment-friendly secondary treatment cost are reduced; the acid making system performs closed operation and conveying on the materials in the whole process, the equipment and the groove body escape gas are concentrated and recovered under negative pressure to be treated by tail gas, and no gas leaks out and no dust exists on site; the system equipment and the pipeline valve mainly adopt corrosion-resistant and high-molecular non-metallic materials, so that long-period operation is guaranteed, and the phenomena of leakage, leakage and leakage are avoided; the purified by-product dilute acid is recycled in the device, and no dilute acid is discharged and subsequent environmental protection treatment is performed; the incineration is equipped with a low-nitrogen combustion technical measure, thereby inhibiting the generation of nitrogen oxides from the source, ensuring the ultralow emission of the nitrogen oxides and improving the quality of sulfuric acid products.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. The method for treating the desulfurization waste liquid and the sulfur foam is characterized by comprising four stages of incineration of the desulfurization waste liquid and the sulfur foam, catalytic oxidation of sulfur dioxide, absorption of sulfur trioxide and absorption of ammonia, and comprises the following steps of:
step 1: feeding the desulfurization waste liquid and sulfur foam generated by ammonia-process coal gas desulfurization into a high-efficiency separation device to separate solid sulfur paste with the water content of less than or equal to 30%, and feeding the sulfur paste into an incinerator by using a screw machine;
step 2: evaporating and concentrating the separated clear liquid to obtain concentrated slurry with concentration of 50-60%, pumping to spray gun, directly spraying into fluidized bed furnace, combusting with sulfur paste in different regions, and combusting with introduced hot air to obtain concentrated slurry containing 6-8% SO2The flue gas of (2);
step 3: based on the steps, after high-temperature dust removal, the waste heat is sent to a waste heat boiler to recover waste heat to generate medium-pressure saturated steam;
step 4: after the hot air heat exchanger and the cold air heat exchanger are used for heating the air entering the furnace, the air is sent to a purification process, and cooling, dehumidification and dehydration of a drying tower are carried out through the purification process;
step 5: based on the steps, preparing an industrial sulfuric acid product by a two-rotation and two-absorption (3+1) acid preparation process;
step 6: returning the industrial sulfuric acid to a desulfurization system of a coking plant to prepare ammonium sulfate;
step 7: and finishing the treatment of the desulfurization waste liquid and the sulfur foam.
2. The method according to claim 1, wherein the desulfurized waste liquid and sulfur foam are transported from the desulfurization unit of the coke-oven plant to the high-efficiency centrifugal device for solid-liquid separation at Step1, and the separated solid sulfur paste has a water content of about 25% and is transported to the acid production area by a transfer vehicle and is transported to the incinerator for combustion by a scraper conveyor and a double-screw (variable frequency) conveyor.
3. The method for treating desulfurized waste liquid and sulfur foams according to claim 1, wherein the clear liquid filtered in Step2 automatically flows to a clear liquid tank in a desulfurization boundary area, is conveyed to a desulfurized waste liquid storage tank in an acid production boundary area by a clear liquid pump through an external pipe network, is conveyed to a condensate water preheater by a desulfurized waste liquid feeding pump, is evaporated and concentrated by a three-effect evaporator, is pumped into a one-effect evaporator by a pump to be evaporated and concentrated continuously, and is conveyed to a concentrated slurry tank by a discharge pump after being evaporated and concentrated continuously by a two-effect evaporator through a pressure difference.
4. The method as claimed in claim 1, wherein the high temperature furnace gas from the incinerator in Step3 is dedusted in the auxiliary combustion chamber, fed into the medium pressure waste heat boiler, the hot air preheater and the cold air preheater for recovering heat, and cooled to about 300 ℃ before being fed into the purification process.
5. The method for treating desulfurized waste liquid and sulfur foams according to claim 1, wherein said Step4 is characterized in that a totally enclosed pickling and purifying process of "dynamic wave-packed tower-two-stage electric demister" is adopted for purifying furnace gas.
6. The method as claimed in claim 1, wherein said Step5 comprises two conversion processes of "3 + 1", using imported high quality catalyst, the conversion rate is controlled to be above 99.85%, and the heat exchange process of conversion is IV, I-III, II.
7. The method as claimed in claim 1, wherein the dilute sulfuric acid solution in Step6 is fed into a regulator, the pH value of the solution is adjusted to about 7 by evaporating condensate in the pretreatment process, a 1-3% dilute ammonium sulfate solution is generated, impurities and iron-aluminum precipitates are removed by three-stage filtration of a precision filter, a cartridge filter and ultrafiltration, clear liquid is fed into an LM membrane group for separation and concentration, ammonium sulfate is concentrated to a concentration of 15-18%, the ammonium sulfate solution is fed into an ammonium sulfate device, clean water produced by the membrane group is internally digested by an acid making system, and the redundant clean water is fed into a desulfurization system to be used as make-up water.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114538385A (en) * | 2021-12-31 | 2022-05-27 | 新兴铸管股份有限公司 | Process for preparing concentrated sulfuric acid from desulfurization waste liquid by dry method |
| 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 |
| CN115539969A (en) * | 2022-10-13 | 2022-12-30 | 山东龙之源节能环保科技有限公司 | Desulfurization waste acid making incineration system |
| CN115818877A (en) * | 2022-12-05 | 2023-03-21 | 山东绿知源环保工程有限公司 | Desulfurization waste liquid pretreatment and incineration system and process |
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2021
- 2021-06-30 CN CN202110733771.1A patent/CN113357652A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114538385A (en) * | 2021-12-31 | 2022-05-27 | 新兴铸管股份有限公司 | Process for preparing concentrated sulfuric acid from desulfurization waste liquid by dry method |
| 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 |
| CN115539969A (en) * | 2022-10-13 | 2022-12-30 | 山东龙之源节能环保科技有限公司 | Desulfurization waste acid making incineration system |
| CN115818877A (en) * | 2022-12-05 | 2023-03-21 | 山东绿知源环保工程有限公司 | Desulfurization waste liquid pretreatment and incineration system and process |
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