CN112707375A - Method for recovering sulfur from sulfuric acid fired by sulfur-containing waste liquid - Google Patents
Method for recovering sulfur from sulfuric acid fired by sulfur-containing waste liquid Download PDFInfo
- Publication number
- CN112707375A CN112707375A CN201911023670.4A CN201911023670A CN112707375A CN 112707375 A CN112707375 A CN 112707375A CN 201911023670 A CN201911023670 A CN 201911023670A CN 112707375 A CN112707375 A CN 112707375A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- waste liquid
- flue gas
- temperature
- sulfur dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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
- C01B17/76—Preparation by contact processes
- C01B17/765—Multi-stage SO3-conversion
- C01B17/7655—Multi-stage SO3-conversion with intermediate absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- 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
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
- C01B17/503—Preparation of sulfur dioxide by reduction of sulfur compounds of sulfuric acid
-
- 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
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
- C01B17/504—Preparation of sulfur dioxide by reduction of sulfur compounds of ammonium sulfates
-
- 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
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/508—Preparation of sulfur dioxide by oxidation of sulfur compounds
-
- 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
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/52—Preparation of sulfur dioxide by roasting sulfides
-
- 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
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/54—Preparation of sulfur dioxide by burning elemental sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for preparing sulfuric acid from sulfur-containing waste liquid and recovering sulfur, wherein the pretreated sulfur-containing waste liquid is sent to an incinerator for combustion, sulfur, elemental sulfur, ammonium sulfate, ammonium thiosulfate, ammonium thiocyanate, sulfide and other sulfur-containing substances are subjected to thermal decomposition and oxidation reaction at high temperature to generate sulfur dioxide-containing furnace gas, the sulfur dioxide-containing furnace gas is subjected to dry filtration and purification, primary conversion and primary absorption to produce a product sulfuric acid product, tail gas is subjected to desulfurization and denitrification treatment and then is discharged up to the standard, the problems of harmless treatment of sulfur-containing waste and efficient recovery of sulfur resources are effectively solved, and a large amount of purified wastewater is avoided. The method has the advantages of short process flow, simple operation, high sulfur recovery and utilization efficiency, high heat recovery efficiency and basically no three wastes in production.
Description
Technical Field
The invention relates to a method for preparing sulfuric acid from sulfur-containing waste liquid and recovering sulfur, belonging to the technical field of environmental protection.
Background
In the production of domestic petrochemical industry, chemical industry, coal chemical industry, coking industry and other industries, a large amount of sulfur-containing waste liquid containing sulfuric acid, elemental sulfur, ammonium sulfate, ammonium thiosulfate, ammonium thiocyanate, sulfide and the like can be produced as byproducts, and the sulfur-containing waste liquid has complex components, inconsistent viscosity and strong corrosivity due to different raw materials and production processes, and belongs to dangerous waste.
At present, solid hazardous waste is formed after the treatment of the waste liquid is basically treated by an acid-base neutralization process, a few waste liquid is concentrated, crystallized, separated and salt-extracted to produce products such as sulfur, ammonium sulfate, ammonium thiosulfate and the like, and the treated waste liquid still needs to be neutralized.
The processes are difficult to harmlessly treat the sulfur-containing waste liquid, have low recovery rate of sulfur resources, high energy consumption and poor economical efficiency, and cause new environmental pollutants.
In China, sulfur dioxide is generated by burning sulfur-containing waste liquid, and then the sulfur dioxide is prepared into sulfuric acid through purification, drying, conversion and absorption, but the following problems exist in the actual production:
the method has the advantages of complex components and properties of the sulfur-containing waste liquid, low sulfur content, high water content and difficult pretreatment;
secondly, the control of the incineration process is difficult, the sulfur dioxide content of the flue gas after incineration is low (the volume concentration is about 5 percent generally), and sulfur-containing raw materials such as sulfur and the like need to be supplemented;
the purification process generates a large amount of dilute sulfuric acid (the mass concentration is generally below 5 percent), and the dilute sulfuric acid is difficult to treat;
the device is small in scale, the general sulfuric acid productivity is below 3 ten thousand tons per year, a two-rotation two-suction acid making process is generally adopted, the process is complex, and the energy efficiency is low;
and the content of sulfur dioxide, nitrogen oxide and sulfuric acid mist particulate matters in the tail gas is high, and the standard emission is difficult.
Disclosure of Invention
The invention provides a method for preparing sulfuric acid from sulfur-containing waste liquid and recovering sulfur, which effectively solves the problems of harmless treatment of sulfur-containing waste and efficient recovery of sulfur resources and avoids the generation of a large amount of purified wastewater.
The main technical scheme of the invention is as follows: a process for reclaiming sulfur from the sulfuric acid generated by burning the waste liquid containing sulfur includes such steps as pretreating the waste liquid containing sulfur, burning in incinerator, thermally decomposing the sulfur-contained substances (sulfuric acid, elementary sulfur, ammonium sulfate, ammonium thiosulfate, ammonium thiocyanate, sulfide, etc) at high temp, oxidizing to obtain the gas containing sulfur dioxide, dry filtering, purifying, converting, absorbing the sulfuric acid product, desulfurizing and denitrifying to obtain tail gas,
the invention discloses a method for recovering sulfur by burning sulfuric acid by typical sulfur-containing waste liquid, which comprises the following steps:
1) sending the sulfur-containing waste liquid with high water content into a spray concentrator for pretreatment, and reducing the water content of the waste liquid to 10-30%;
2) sending the pretreated sulfur-containing waste liquid into an incinerator, and thermally decomposing the sulfur-containing waste liquid into sulfur dioxide-containing flue gas at the temperature of 800-1200 ℃;
3) high-temperature sulfur dioxide-containing flue gas discharged from the incinerator enters a waste heat boiler to recover heat energy, medium-pressure steam is obtained as a byproduct, and then the flue gas enters an air preheater to preheat air and is cooled to 500-600 ℃;
4) removing solid particles from the sulfur dioxide-containing flue gas cooled in the step 3) by using a cyclone dust collector, a filter and other filtering equipment, and sending the sulfur dioxide-containing flue gas at the temperature of 420 ℃ to a converter;
5) in the converter, sulfur dioxide is oxidized under the action of a vanadium catalyst to generate sulfur trioxide, and the sulfur trioxide flue gas is sent into an absorption tower to produce sulfuric acid after being cooled;
6) and 5) feeding the flue gas absorbed in the step 5) into a desulfurizing tower, and feeding the desulfurized flue gas into a chimney for discharging.
Preferably, in the method for recovering sulfur by incinerating sulfuric acid with a sulfur-containing waste liquid, in the step 1), high-temperature air at 500 to 600 ℃ from an air preheater is used as a heat source, and the water content of the sulfur-containing waste liquid is reduced to 30% or less in a spray concentrator.
Preferably, in the method for recovering sulfur by incinerating sulfuric acid with the sulfur-containing waste liquid, in the step 2), the sulfur-containing waste liquid with the temperature of 120-140 ℃ is pumped into an incinerator and sprayed into the incinerator through an atomizing spray gun; in the incinerator, coke oven gas, natural gas, sulfur-containing organic waste gas and the like are used as combustion heat sources, high-temperature air at 500-600 ℃ from an air preheater is used as combustion-supporting air, and sulfur-containing waste liquid is thermally decomposed into sulfur dioxide at the temperature of 800-1200 ℃.
Preferably, in the method for recovering sulfur by burning sulfuric acid with the sulfur-containing waste liquid, in the step 3), high-temperature sulfur-containing flue gas discharged from the incinerator enters an on-line ash removal type fire tube waste heat boiler to recover heat energy and byproduct medium-pressure steam, and the flue gas after being cooled enters a high-efficiency air preheater to preheat air and is cooled to 450-550 ℃; and (3) preheating high-temperature air at 500-600 ℃, wherein one path of air is sent to a spray concentration system, and the other path of air is sent to an incinerator.
Preferably, in the method for recovering sulfur by burning sulfuric acid with the sulfur-containing waste liquid, in the step 4), sulfur dioxide-containing flue gas from an air preheater is subjected to cyclone dust removal to remove large-particle-size particles, and then enters a high-temperature-resistant precision filter such as a ceramic membrane filter to remove micron-sized solid particles, the sulfur dioxide-containing flue gas with the temperature reduced to 420 ℃ is sent to a converter to be converted to generate sulfur trioxide-containing flue gas, and the sulfur trioxide-containing flue gas is sent to an absorption tower to be absorbed by concentrated sulfuric acid to generate the product sulfuric acid.
Preferably, in the method for recovering sulfur by incinerating sulfuric acid with a sulfur-containing waste liquid, in the step 6), dilute ammonia water and hydrogen peroxide are used as absorbents in a desulfurizing tower, sulfur dioxide in flue gas is reduced to the requirements of emission standards, and then acid mist is removed by a demister and then the flue gas is emptied from a chimney. The first-stage tail absorption tower uses dilute ammonia water as an absorbent, and the byproduct ammonium sulfate desulfurization solution is recycled; the secondary tail absorption tower uses hydrogen peroxide as an absorbent, and the byproduct dilute sulfuric acid is recycled.
Preferably, dilute ammonia water with the mass concentration of 5-15% is used as an absorbent, sulfur dioxide in the tail gas is absorbed to generate mixed liquid of ammonium sulfite and ammonium sulfate, and the mixed liquid is returned to production and recycling; hydrogen peroxide with the mass concentration of 5-10% is used as an absorbent to further absorb sulfur dioxide and particulate matters in the tail gas, and dilute sulfuric acid with the mass concentration of 20-40% is returned to the absorption process to be used as make-up water for recycling.
Preferably, the sulfuric acid mist aerosol and the solid particles in the tail gas are removed by a wet electric demister.
The invention has the beneficial effects that the dry-method filtering and dust removing process is adopted, the waste heat boiler and the air preheater are utilized to recover heat energy, and the heat energy utilization efficiency is high; the method adopts a one-time conversion and one-time absorption acid making process and a dilute ammonia water and hydrogen peroxide two-stage desulfurization process, has short process flow, simple operation, high sulfur recycling efficiency and basically no three wastes in production.
Drawings
FIG. 1 is a schematic process flow diagram of a method according to an embodiment of the present invention.
In the figure, 1-dilute sulfur-containing waste liquid storage tank, 2-spray concentrator, 3-sulfur-containing waste liquid storage tank, 4-incinerator, 5-fuel storage tank, 6-waste heat boiler, 7-air preheater, 8-air fan, 9-cyclone dust collector, 10-ceramic membrane filter, 11-converter, 12-absorption tower, 13-finished acid storage tank, 14-primary tail absorption tower, 15-dilute ammonia water storage tank, 16-ammonium sulfate storage tank, 17-secondary tail absorption tower, 18-hydrogen peroxide storage tank, 19-wet electric demister and 20-chimney.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
In the following embodiment, a certain characteristic industrial sulfur-containing waste liquid is used as a raw material, natural gas or coke oven gas is used as a fuel, preheated air is used for supporting combustion, and the sulfur-containing waste liquid is subjected to spray concentration pretreatment and incineration to prepare acid, so that high-quality product sulfuric acid is generated from the sulfur-containing waste liquid, and efficient utilization of sulfur resources is realized.
Referring to the attached figure 1, high-temperature air from an air preheater is used as a heat source, the water content of the sulfur-containing waste liquid is reduced to 10-30% in a spray concentrator, the sulfur-containing waste liquid from the spray concentrator is sent into an incinerator by a pump and is sprayed into the incinerator by an atomizing spray gun; coke oven gas, natural gas, sulfur-containing organic waste gas and the like are used as combustion heat sources in the incinerator, high-temperature air from the air preheater is used as combustion-supporting air, sulfur-containing waste liquid is thermally decomposed into sulfur dioxide at the temperature of 800-1200 ℃, high-temperature sulfur dioxide-containing flue gas from the incinerator enters a waste heat boiler and a high-efficiency air preheater to recover heat energy, and then is subjected to dry purification and one-by-one conversion to produce sulfuric acid.
In the embodiment, the high-temperature sulfur dioxide-containing flue gas from the incinerator is subjected to a dry purification process, a cyclone dust collector is used for removing large-particle-size particles, and a precise ceramic membrane filter is used for removing micron-sized solid particles; the acid preparation adopts a primary conversion and a primary absorption process, tail gas at the outlet of an absorption tower respectively adopts a two-stage absorption process, a first-stage desulfurizing tower uses dilute ammonia water as an absorbent, and a byproduct ammonium sulfate desulfurizing liquid is recycled; the secondary desulfurizing tower uses hydrogen peroxide as an absorbent, and the byproduct dilute sulfuric acid is recycled.
In the embodiment, the atomized sulfur-containing waste liquid with the water content of 10-30% by mass, combustion-supporting air at 500-600 ℃ and auxiliary fuel are sprayed into the incinerator, the temperature of the decomposing furnace is controlled at 800-1200 ℃, the decomposing furnace is operated under micro negative pressure, the oxygen volume concentration of furnace gas at an outlet of the incinerator is 2-3%, and the auxiliary fuel can be at least one of coke oven gas, natural gas, liquefied petroleum gas, water gas and hydrogen sulfide.
The embodiment adopts heat exchange equipment such as an on-line ash removal type fire tube waste heat boiler, a shell-and-tube air preheater and the like to recover the heat energy of the system, and the temperature of the flue gas at the outlet of the air preheater is controlled to be 450-550 ℃.
In the embodiment, the flue gas at the outlet of the incinerator adopts a dry filtering and dust removing technology, the sulfur dioxide-containing flue gas firstly passes through a cyclone dust collector to remove large-particle-size particles, then enters a high-temperature-resistant precise ceramic membrane to filter and remove micron-sized solid particles, and the sulfur dioxide-containing flue gas with the temperature reduced to 420 ℃ is sent to a converter to be converted.
The embodiment of the acid making system adopts a one-time conversion and one-time absorption contact method acid making process, sulfur dioxide-containing flue gas enters a three-section bed layer converter filled with a cesium-vanadium-containing catalyst for oxidation reaction, and the generated sulfur trioxide-containing flue gas enters an absorption tower to generate sulfuric acid as a product.
In the embodiment, dilute ammonia water and hydrogen peroxide are used as absorbents in the desulfurizing tower, sulfur dioxide in flue gas is reduced to the requirement of emission standard, and then acid mist is removed by a demister and then the flue gas is emptied from a chimney. The primary tail absorption tower uses dilute ammonia water with the mass concentration of 5-15% as an absorbent, and the byproduct ammonium sulfate desulfurization solution is recycled; the secondary tail absorption tower uses 5-10% of hydrogen peroxide as an absorbent, and the byproduct of dilute sulfuric acid with 20-40% of mass concentration is returned to the absorption process for recycling of make-up water. And (3) removing sulfuric acid mist aerosol and solid particles in the tail gas by adopting a wet-type electric demister.
Example 1
Treating certain sulfur-containing waste liquid with the flow rate of 2.7t/h and the normal temperature of 25 ℃; the sulfur-containing waste liquid contains 16.00 percent of elemental sulfur, 14.57 percent of ammonium thiocyanate, 7.29 percent of ammonium thiosulfate, 0.46 percent of ammonium sulfide, 1.97 percent of ammonium sulfite, 2.41 percent of ammonium sulfate, 0.88 percent of ammonium carbonate, 0.15 percent of ammonia and 56.27 percent of water. The fuel is coke oven gas, and the combustion-supporting air is preheated air at 600 ℃. The air entering the spray concentrator has the temperature of 600 ℃ and the flow rate of 2000 m3H is used as the reference value. The sulfur-containing waste liquid enters an outlet of the spray concentrator and is 1.5 t/h, and the water content is 20 percent. The sulfur-containing waste liquid, preheated air at 600 ℃ and a proper amount of coke oven gas enter equipment 4 for incineration, the incineration temperature is controlled at 1100 ℃, and the flow of furnace gas at the outlet of the equipment 4 is 12000 m3And h, the oxygen concentration of furnace gas is 2 percent, the sulfur dioxide concentration is 5 percent, and the industrial sulfuric acid product is produced by dry purification, primary conversion and primary absorption for 2.2 t/h.
Example 2
Treating certain sulfur-containing waste liquid at the normal temperature of 25 ℃ at the flow rate of 3.2 t/h; the sulfur-containing waste liquid contains 15.99% of elemental sulfur, 6.78% of ammonium thiocyanate, 3.89% of ammonium thiosulfate, 3.39% of ammonium sulfide, 0.37% of ammonium sulfite, 1.58% of ammonium sulfate, 1.93% of ammonium carbonate, 0.15% of ammonia and 68.96% of water. The fuel is coke oven gas, and the combustion-supporting air is preheated air at 500 ℃. Air entering the spray concentrator is at 500 ℃ and 3000 m in flow3H is used as the reference value. The sulfur-containing waste liquid enters an outlet of the spray concentrator and is 1.3 t/h, and the water content is 15 percent. The sulfur-containing waste liquid, preheated air at 500 ℃ and a proper amount of coke oven gas enter equipment 4 for incineration, the incineration temperature is controlled to be 1000 ℃, and an outlet furnace of the equipment 4 is used13000 m of air flow3The oxygen concentration of furnace gas is 2.5 percent and the sulfur dioxide concentration is 6 percent, and industrial sulfuric acid products are produced by dry purification, primary conversion and primary absorption for 2.3 t/h.
Example 3
Treating certain sulfur-containing waste liquid with the flow rate of 5t/h and the normal temperature of 25 ℃; the mass fraction of ammonium sulfate in the sulfur-containing waste liquid is 19%, the mass fraction of sodium sulfate is 2.6%, the mass fraction of sulfuric acid is 5.1%, the mass fraction of ammonium acetone sulfonate is 42%, and the mass fraction of water is 36.3%. The fuel is natural gas, and the combustion air is preheated air at 500 ℃. Air entering the spray concentrator is at 500 ℃ and 3000 m in flow3H is used as the reference value. The outlet of the spray concentrator is 4t/h of sulfur-containing waste liquid with 20 percent of water. The sulfur-containing waste liquid, preheated air at 500 ℃ and a proper amount of natural gas enter equipment 4 for incineration, the incineration temperature is controlled to be 1200 ℃, and the flow of furnace gas at the outlet of the equipment 4 is 10000 m3And h, the oxygen concentration of furnace gas is 2 percent, the sulfur dioxide concentration is 5 percent, and industrial sulfuric acid products are produced by dry purification, primary conversion and primary absorption for 2 t/h.
Claims (9)
1. A method for preparing sulfuric acid from sulfur-containing waste liquid and recovering sulfur is characterized in that the pretreated sulfur-containing waste liquid is sent to an incinerator for combustion, sulfur-containing substances are subjected to thermal decomposition and oxidation reaction at high temperature to generate sulfur dioxide-containing furnace gas, the sulfur dioxide-containing furnace gas is subjected to dry filtering, purification, conversion and absorption to produce product-grade sulfuric acid products, and tail gas is subjected to desulfurization and denitrification treatment and then is discharged after reaching standards.
2. The method according to claim 1, characterized by comprising the steps of:
1) sending the sulfur-containing waste liquid with high water content into a spray concentrator for pretreatment, and reducing the water content of the waste liquid to 10-30%;
2) sending the pretreated sulfur-containing waste liquid into an incinerator, and thermally decomposing the sulfur-containing waste liquid into sulfur dioxide-containing flue gas at the temperature of 800-1200 ℃;
3) high-temperature sulfur dioxide-containing flue gas discharged from the incinerator enters a waste heat boiler to recover heat energy, medium-pressure steam is obtained as a byproduct, and then the flue gas enters an air preheater to preheat air and is cooled to 500-600 ℃;
4) removing dust and solid particles from the sulfur dioxide-containing flue gas cooled in the step 3) by filtering, and sending the sulfur dioxide-containing flue gas at the temperature of 420 ℃ to a converter;
5) in the converter, sulfur dioxide is oxidized under the action of a vanadium catalyst to generate sulfur trioxide, and the sulfur trioxide flue gas is sent into an absorption tower to produce sulfuric acid after being cooled;
6) and 5) feeding the flue gas absorbed in the step 5) into a desulfurizing tower, and feeding the desulfurized flue gas into a chimney for discharging.
3. The method according to claim 2, wherein in the step 1), the water content of the sulfur-containing waste liquid is reduced in a spray concentrator by using high-temperature air with a temperature of 500-600 ℃ from an air preheater as a heat source.
4. The method according to claim 2, wherein in the step 2), the sulfur-containing waste liquid with the temperature of 120-140 ℃ is pumped into the incinerator and is sprayed into the incinerator through an atomizing spray gun; coke oven gas, natural gas and sulfur-containing organic waste gas are used as combustion heat sources in the incinerator, high-temperature air at 500-600 ℃ from an air preheater is used as combustion-supporting air, and sulfur-containing waste liquid is thermally decomposed into sulfur dioxide at the temperature of 800-1200 ℃.
5. The method according to claim 2, characterized in that in the step 3), the high-temperature sulfur-containing flue gas from the incinerator enters an on-line ash removal type fire tube waste heat boiler to recover heat energy and byproduct medium-pressure steam, and the flue gas after being cooled enters a high-efficiency air preheater to preheat air and is cooled to 450-550 ℃; and (3) preheating high-temperature air at 500-600 ℃, wherein one path of air is sent to a spray concentration system, and the other path of air is sent to an incinerator.
6. The method as claimed in claim 2, wherein in the step 4), the sulfur dioxide-containing flue gas from the air preheater is subjected to cyclone dust removal to remove large-particle-size particles, and then enters a ceramic membrane filter to remove micron-sized solid particles, and the sulfur dioxide-containing flue gas with the temperature reduced to 420 ℃ is sent to a converter for conversion.
7. The method according to claim 2, wherein in the step 6), dilute ammonia water and hydrogen peroxide are used as absorbents in the desulfurizing tower, sulfur dioxide in the flue gas is reduced to the emission standard, and then the flue gas is subjected to demister to remove acid mist and then is emptied from a chimney.
8. The method according to claim 7, characterized in that dilute ammonia water with a mass concentration of 5% -15% is used as an absorbent, sulfur dioxide in tail gas is absorbed to generate mixed solution of ammonium sulfite and ammonium sulfate, and the mixed solution is returned to production and recycling; hydrogen peroxide with the mass concentration of 5-10% is used as an absorbent to further absorb sulfur dioxide and particulate matters in the tail gas, and dilute sulfuric acid with the mass concentration of 20-40% is returned to the absorption process to be used as make-up water for recycling.
9. The method of claim 1, wherein the sulfuric acid mist aerosol and the solid particulate matter in the exhaust gas are removed by a wet electric demister.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911023670.4A CN112707375A (en) | 2019-10-25 | 2019-10-25 | Method for recovering sulfur from sulfuric acid fired by sulfur-containing waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911023670.4A CN112707375A (en) | 2019-10-25 | 2019-10-25 | Method for recovering sulfur from sulfuric acid fired by sulfur-containing waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112707375A true CN112707375A (en) | 2021-04-27 |
Family
ID=75540717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911023670.4A Pending CN112707375A (en) | 2019-10-25 | 2019-10-25 | Method for recovering sulfur from sulfuric acid fired by sulfur-containing waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112707375A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113511634A (en) * | 2021-05-08 | 2021-10-19 | 佛山市景嘉机电设备有限公司 | System and method for preparing sulfuric acid by recycling waste ferric sulfate crude salt in acid washing of steel industry |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355132A (en) * | 2000-12-01 | 2002-06-26 | 余振耀 | Process for preparing sulfuric acid |
| CN101092577A (en) * | 2007-04-16 | 2007-12-26 | 中冶焦耐工程技术有限公司 | Technique and equipment for preparing sulfuric acid by using sulfur and waste liquid generated from coal gas wet type oxidation sweetening technique |
| CN101561144A (en) * | 2008-08-21 | 2009-10-21 | 周开根 | Clean incineration system of refuse and organic wastes and device thereof |
| CN104785091A (en) * | 2015-04-24 | 2015-07-22 | 南京澄天环境科学研究院有限公司 | Advanced emission reduction method and device for sulfur-containing tail gas of fuming furnace |
| CN104998530A (en) * | 2015-03-31 | 2015-10-28 | 武汉宇青环保科技有限公司 | Sulfuric acid tail gas desulphurization device and method |
| CN105056722A (en) * | 2015-07-29 | 2015-11-18 | 华中科技大学 | Method for removing multiple flue gas pollutants of coal fired boiler integrally and system thereof |
| CN105209381A (en) * | 2013-03-15 | 2015-12-30 | Mecs公司 | Recovery of sulfur trioxide heat of absorption |
| CN105457463A (en) * | 2014-09-09 | 2016-04-06 | 江苏澄天环保科技有限公司 | Method and device for deep emission reduction of sulfur-bearing exhaust gas |
| CN106379868A (en) * | 2016-08-30 | 2017-02-08 | 南京海陆化工科技有限公司 | Method for preparing sulfuric acid by burning sulfur-containing waste liquid |
| CN106430116A (en) * | 2016-08-24 | 2017-02-22 | 金能科技股份有限公司 | Method for preparing sulfuric acid by utilizing sulfur-containing waste liquid generated during gas wet type oxidation process |
| CN109852434A (en) * | 2019-02-20 | 2019-06-07 | 宁波科新化工工程技术有限公司 | A kind of method of coke-oven-gas desulfurization and decyanation concentration relieving haperacidity |
| CN110282606A (en) * | 2019-07-05 | 2019-09-27 | 科洋环境工程（上海）有限公司 | The wet processing system and technique of aqueous sulphur cream and desulfurization waste liquor |
-
2019
- 2019-10-25 CN CN201911023670.4A patent/CN112707375A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355132A (en) * | 2000-12-01 | 2002-06-26 | 余振耀 | Process for preparing sulfuric acid |
| CN101092577A (en) * | 2007-04-16 | 2007-12-26 | 中冶焦耐工程技术有限公司 | Technique and equipment for preparing sulfuric acid by using sulfur and waste liquid generated from coal gas wet type oxidation sweetening technique |
| CN101561144A (en) * | 2008-08-21 | 2009-10-21 | 周开根 | Clean incineration system of refuse and organic wastes and device thereof |
| CN105209381A (en) * | 2013-03-15 | 2015-12-30 | Mecs公司 | Recovery of sulfur trioxide heat of absorption |
| CN105457463A (en) * | 2014-09-09 | 2016-04-06 | 江苏澄天环保科技有限公司 | Method and device for deep emission reduction of sulfur-bearing exhaust gas |
| CN104998530A (en) * | 2015-03-31 | 2015-10-28 | 武汉宇青环保科技有限公司 | Sulfuric acid tail gas desulphurization device and method |
| CN104785091A (en) * | 2015-04-24 | 2015-07-22 | 南京澄天环境科学研究院有限公司 | Advanced emission reduction method and device for sulfur-containing tail gas of fuming furnace |
| CN105056722A (en) * | 2015-07-29 | 2015-11-18 | 华中科技大学 | Method for removing multiple flue gas pollutants of coal fired boiler integrally and system thereof |
| CN106430116A (en) * | 2016-08-24 | 2017-02-22 | 金能科技股份有限公司 | Method for preparing sulfuric acid by utilizing sulfur-containing waste liquid generated during gas wet type oxidation process |
| CN106379868A (en) * | 2016-08-30 | 2017-02-08 | 南京海陆化工科技有限公司 | Method for preparing sulfuric acid by burning sulfur-containing waste liquid |
| CN109852434A (en) * | 2019-02-20 | 2019-06-07 | 宁波科新化工工程技术有限公司 | A kind of method of coke-oven-gas desulfurization and decyanation concentration relieving haperacidity |
| CN110282606A (en) * | 2019-07-05 | 2019-09-27 | 科洋环境工程（上海）有限公司 | The wet processing system and technique of aqueous sulphur cream and desulfurization waste liquor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113511634A (en) * | 2021-05-08 | 2021-10-19 | 佛山市景嘉机电设备有限公司 | System and method for preparing sulfuric acid by recycling waste ferric sulfate crude salt in acid washing of steel industry |
| CN113511634B (en) * | 2021-05-08 | 2023-11-10 | 佛山市景嘉机电设备有限公司 | System and method for preparing sulfuric acid by recycling waste ferric sulfate crude salt in steel industry through pickling |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7075910B2 (en) | Acid gas treatment | |
| CN111285335B (en) | System for preparing sulfuric acid by using sulfur foam and desulfurization waste liquid semidry method and acid preparation method | |
| CN109482049B (en) | Dry desulfurization, denitrification and purification integrated process for coke oven flue gas | |
| CN102489149A (en) | Flue-gas purification and reclamation system and method thereof | |
| CN105214478A (en) | The integral process of a kind of coke oven flue exhuast gas desulfurization denitration and waste heat recovery | |
| CN109928415B (en) | System and method for recovering calcium carbonate and sulfur by calcining gypsum | |
| CN109052335A (en) | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid | |
| CN210523360U (en) | Processing system for waste salt resourceful treatment | |
| CN106379868A (en) | Method for preparing sulfuric acid by burning sulfur-containing waste liquid | |
| CN110894064A (en) | Device and method for preparing sulfuric acid by cracking and regenerating waste sulfuric acid and/or sulfur-containing waste liquid | |
| CN112898999A (en) | Catalytic pyrolysis-oxidation multi-stage furnace treatment integrated device and method for waste salt containing organic pollutants | |
| CN110332552B (en) | Resourceful treatment system and method for chlorine-sulfur-containing organic waste liquid | |
| CN109592647B (en) | Process for preparing sulfur and recovering desulfurizing/nitre agent by sulfur/nitrate iron-carbon reduction | |
| CN108654363B (en) | Acid making process by coupling waste heat of coke oven flue gas and sulfur pollutants | |
| CN110683520B (en) | Process for preparing sulfuric acid by regenerating low-concentration dilute waste sulfuric acid | |
| CN206463781U (en) | A kind of desulfuring and denitrifying apparatus of coke oven flue gas | |
| CN112707375A (en) | Method for recovering sulfur from sulfuric acid fired by sulfur-containing waste liquid | |
| CN210523361U (en) | Waste salt resourceful treatment processing system | |
| CN1636866A (en) | Combined dry and wet process of preparing high concentration sulfuric acid with hydrogen sulfide | |
| CN209161488U (en) | A kind of system of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid | |
| CN109939550B (en) | Method and device for treating FCC (fluid catalytic cracking) regenerated flue gas | |
| CN108178132B (en) | Sulfur recovery method and equipment in carbon disulfide production | |
| CN104876190A (en) | Oxygen-enriched combustion-supporting waste acid cracking process | |
| CN211694934U (en) | High-sulfur waste gas rich combustion device | |
| CN112158840B (en) | System and method for high-sulfur high-oxygen smelting flue gas tempering and carbon material activation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210427 |
|
| RJ01 | Rejection of invention patent application after publication |