CN110683520A - Process for preparing sulfuric acid by regenerating low-concentration dilute waste sulfuric acid - Google Patents
Process for preparing sulfuric acid by regenerating low-concentration dilute waste sulfuric acid Download PDFInfo
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- CN110683520A CN110683520A CN201810737282.1A CN201810737282A CN110683520A CN 110683520 A CN110683520 A CN 110683520A CN 201810737282 A CN201810737282 A CN 201810737282A CN 110683520 A CN110683520 A CN 110683520A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/80—Apparatus
- C01B17/806—Absorbers; Heat exchangers
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
Compared with the traditional acid-base neutralization and dilute waste acid multi-effect concentration treatment process, the spray concentration pretreatment and high-temperature cracking acid preparation process can treat various dilute sulfuric acids, and recovers and utilizes 5% to ~ 15% of dilute sulfuric acid produced in the dilute acid cleaning process and 20% to ~ 40% of dilute sulfuric acid produced in tail gas desulfurization, thereby improving the sulfur recovery rate and the heat energy recovery rate and greatly reducing the operation cost of the device.
Description
Technical Field
The invention belongs to the technical field of chemical industry and environmental protection, and particularly relates to a process for preparing sulfuric acid by regenerating low-concentration dilute waste sulfuric acid.
Background
The sulfuric acid is applied to unit operations such as esterification, sulfonation, alkylation, purification and dehydration, most of sulfuric acid is changed into dilute waste sulfuric acid with the mass concentration of below 50%, and the dilute waste sulfuric acid contains a large amount of organic impurities and inorganic impurities, is toxic and harmful, emits odor and is very difficult to treat. The industries such as dye, organic fine chemical industry, titanium pigment, secondary lead and the like in China generate a large amount of dilute waste sulfuric acid with the mass concentration of below 50 percent, and the total amount per year is close to 1000 ten thousand tons. At present, the part of dilute waste sulfuric acid is classified as dangerous waste and needs to be treated urgently. The common treatment process of the dilute waste sulfuric acid is an alkali neutralization method and a multi-effect concentration method, and the sulfuric acid is changed into solid waste residue containing sulfate by the alkali neutralization, so that secondary pollution is easily caused. The multi-effect concentration method uses steam as a heat source to concentrate the dilute waste sulfuric acid to a certain concentration for recovery, organic impurities and inorganic impurities in the dilute waste sulfuric acid directly influence the process operation, and the concentrated acid has low concentration, poor quality, difficult effective utilization and high operation cost. The domestic development of the waste sulfuric acid cracking regeneration technology can only treat concentrated sulfuric acid with the mass concentration of more than 80%, and the economical efficiency of treating dilute waste sulfuric acid with the mass concentration of less than 50% is poor. The process for preparing sulfuric acid by regenerating low-concentration dilute waste sulfuric acid combines the technical advantages of spray concentration and pyrolysis, utilizes the reliable heat source of an acid preparation system to concentrate the dilute waste sulfuric acid to the economic recovery concentration of more than 80%, and produces high-quality industrial sulfuric acid products by pyrolysis. The process technology has large treatment capacity of dilute waste sulfuric acid, and the scale of a single set of device can reach the sulfuric acid yield of 10 ten thousand tons per year. The investment and the operation cost of the process technology are very competitive, and the process has good economic benefit and environmental benefit.
Based on the consideration of recycling of sulfur resources and comprehensive recovery of resources, the inventor provides a new technology for spraying and concentrating dilute waste sulfuric acid with the mass concentration of below 50% to the concentration of above 80% by utilizing the heat energy of cracking furnace gas, and then spraying concentrated sulfuric acid, preheated air and fuel into a cracking furnace to prepare acid. The reports of patent and research literature of the method are not found.
Disclosure of Invention
The invention relates to a process for preparing sulfuric acid by regenerating low-concentration dilute waste sulfuric acid. The invention integrates the processes of spraying concentration and pyrolysis of the dilute waste sulfuric acid, and realizes the recycling of the dilute waste sulfuric acid and sulfur resources.
The method is mainly characterized in that dilute waste sulfuric acid containing organic matters and inorganic matters and having the mass concentration of less than 50% of industrial by-products is comprehensively recycled, the method is characterized in that dilute waste sulfuric acid spray concentration process with the mass concentration of 400 ~ ℃ decomposing furnace gas as a concentration heat source is adopted, low-concentration dilute waste sulfuric acid having the mass concentration of less than 50% and dilute sulfuric acid having the mass concentration of 5% 3615% generated in an acid preparation purification process are concentrated and concentrated by controlling the gas-liquid ratio of a spray concentration tower, the generated concentrated waste sulfuric acid having the mass concentration of more than 80% is sent into a decomposing furnace, gas discharged from the spray concentration tower is merged into furnace gas at an outlet of an air preheater, the gas is mixed and combusted with preheated combustion-supporting air and fuel at 300 39500 ℃ in the decomposing furnace, the concentrated waste sulfuric acid is thermally decomposed into high-temperature furnace gas containing sulfur dioxide, sulfur trioxide, water, oxygen, nitrogen, carbon dioxide and other impurities, the high-temperature furnace gas is subjected to heat energy recovery by a waste heat boiler and an air preheater to generate steam, the furnace gas from the 400 ~ ℃ decomposing furnace gas from the waste decomposing furnace gas at the waste furnace gas from the waste gas, one path of the waste gas is sent into air preheater, the flue gas is sequentially sent into a dilute waste sulfuric acid preparation process of a dilute waste sulfuric acid purification process, the dilute acid, the tail gas with.
The invention is suitable for the working condition that the concentration and the flow of the dilute waste sulfuric acid fluctuate greatly, the mass concentration of the dilute waste sulfuric acid can be 5 percent ~ 50 percent, and the flow can fluctuate at 50 percent ~ 120 percent.
The invention relates to a process for preparing sulfuric acid by regenerating low-concentration dilute waste sulfuric acid, which comprises the working procedures of spraying and concentrating the dilute waste sulfuric acid, filtering the concentrated waste sulfuric acid, burning the concentrated waste sulfuric acid, recovering waste heat, carrying out dilute acid cleaning and purification on furnace gas, converting, drying and absorbing, desulfurizing and denitrating tail gas and the like, and produces industrial sulfuric acid products with the mass concentration of 98%.
The invention adopts a gas-liquid countercurrent spray concentration process of high-temperature gas mass transfer and heat transfer to concentrate industrial dilute waste sulfuric acid containing organic matters and inorganic matters with the mass fraction of less than 50 percent to the mass fraction of more than 80 percent, and the temperature of the high-temperature gas is 400 ~ 500 ℃ of the furnace gas of a decomposing furnace.
The concentrated waste sulfuric acid discharged from the spray concentration tower is subjected to solid-liquid separation to remove organic and inorganic impurities in the concentrated waste sulfuric acid, the separated sulfuric acid liquid is sent to a decomposing furnace for thermal decomposition, after gas discharged from the spray concentration tower is subjected to gas-liquid separation, a part of gas returns to the spray concentration tower for adjusting the inlet gas temperature, and a part of gas is merged into the furnace gas at the outlet of an air preheater for preparing acid.
The atomized concentrated waste sulfuric acid with the mass fraction of more than 80%, combustion-supporting air and auxiliary fuel are sprayed into the decomposing furnace, the temperature of the decomposing furnace is controlled at 1000 ~ 1200 ℃, the micro negative pressure operation is carried out, the oxygen volume concentration of furnace gas at the outlet of the decomposing furnace is 1% ~ 3%, the combustion-supporting air is preheated to 300 ~ 500 ℃, and the auxiliary fuel can be natural gas, liquefied petroleum gas, coke oven gas, water gas, sulfur, hydrogen sulfide and the like.
The decomposing furnace is of a steel shell lining refractory brick structure and can be a horizontal furnace type or a vertical furnace type, secondary air is arranged in the decomposing furnace, and an ash discharging system is arranged at the tail end of the decomposing furnace.
The acid making system adopts a contact method acid making process, adopts the processes of twice conversion and twice absorption, and comprises a waste heat recovery process, a dilute acid cleaning and purifying process, a dry absorption process of spraying and drying sulfuric acid with the mass concentration of 93 percent and spraying and absorbing sulfuric acid with the mass concentration of 98 percent, a conversion process and a tail gas desulfurization process.
The dilute sulfuric acid with the mass concentration of 5 percent ~ 15 percent is generated in the dilute acid cleaning process, the dilute sulfuric acid contains inorganic impurities, the dilute sulfuric acid is subjected to solid-liquid filtration, the dilute sulfuric acid is sent to a spray concentration tower for concentration treatment to recover sulfur resources, the filtered solid slag is sent to a slag yard, and no acid wastewater is generated in an acid making system.
The invention is provided with a waste heat boiler and an air preheater at the outlet of the decomposing furnace, recovers the waste heat of high-temperature furnace gas at the outlet of the decomposing furnace, controls the temperature of the furnace gas to be 30 ℃ higher than the dew point temperature of the furnace gas, and enters a dilute pickling purification process, the waste heat boiler produces steam, the conversion process is provided with the air preheater for recovering the waste heat of high-temperature converted gas, heats the air to 200 ℃, the preheated air is sent to the waste heat boiler, then the air preheater is continuously heated to 400 ~ 500 ℃, the preheated air is sent to the decomposing furnace to be used as combustion-supporting air, and the waste heat produced by an acid making system is utilized to.
The tail gas discharged by the second-stage absorption tower of the acid making system is subjected to large particle acid mist removal by the fiber demister and then is sent into the tail gas desulfurization tower, the acid making tail gas is treated by adopting a hydrogen peroxide oxidation desulfurization and denitrification process, and the desulfurized gas is further subjected to sulfuric acid mist removal by the electric demister to reach SO2The mass concentration is less than 100 mg/m3The mass concentration of nitrogen oxide is less than 50 mg/m3The mass concentration of the sulfuric acid mist is less than 30 mg/m3The desulfurization by-product generated by the hydrogen peroxide oxidation method is dilute sulfuric acid with the mass fraction of 20 percent ~ 40 percent, most of the dilute sulfuric acid is returned to the dry absorption process for recycling, and the small part of the dilute sulfuric acid is sent to a spray concentration tower for concentration treatment.
Drawings
FIG. 1 is a schematic process flow diagram of an embodiment of the present invention.
In the figure, 1-dilute waste sulfuric acid storage tank, 2-spray concentration tower, 3-gas-liquid separator, 4-concentrated waste sulfuric acid storage tank, 5-liquid filter, 6-decomposing furnace, 7-fuel storage tank, 8-ash storage bin, 9-waste heat boiler, 10-gas filter, 11-air preheater, 12-air fan, 13-purification washer, 14-purified dilute acid storage tank, 15-dilute acid filter, 16-electric demister, 17-SO2The method comprises the following steps of a main fan, 18-a drying tower, 19-a converter, 20-a first-stage absorption tower, 21-a finished acid storage tank, 22-a second-stage absorption tower, 23-a desulfurizing tower and 24-a 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 embodiments, several kinds of characteristic industrial dilute waste sulfuric acid are respectively used as raw materials, natural gas is used as fuel, preheated air is used for supporting combustion, acid is prepared by spray concentration pretreatment and pyrolysis, and the dilute waste sulfuric acid is used for generating high-quality product sulfuric acid, so that efficient utilization of sulfur resources is realized.
Referring to the attached drawing 1, the process flow of the invention adopts the following process flow that dilute waste sulfuric acid with the mass concentration of 5% ~% enters the equipment 1 in the drawing 1, 5% ~% dilute sulfuric acid with the mass concentration from the equipment 15 is added into the equipment 1, the dilute sulfuric acid in the equipment 1 is fed into the equipment 2 by a pump and is atomized from top to bottom by an air flow nozzle and is in countercurrent contact with hot furnace gas entering from the lower part of the equipment 2, gas-liquid mass transfer and heat transfer are carried out, the hot furnace gas brings most of water in the dilute waste sulfuric acid out of the equipment 2, 80% concentrated sulfuric acid with the mass concentration discharged from the bottom of the equipment 2 enters the equipment 4, the concentrated sulfuric acid with the mass concentration of 80% is fed into the top of the equipment 6 by an atomizing spray gun after impurity removal by the equipment 5, the gas discharged from the equipment 2 is filtered by the equipment 3 to remove sulfuric acid mist, one path is fed into the equipment 2 for circulation, the inlet treatment of the equipment 13, natural gas and hot air with the temperature of 300 ~ ℃ is sprayed into the upper part of the equipment 6, the tower is controlled at 1000 ~ ℃, the tail gas temperature of the tail gas is completely decomposed by the equipment 6, the tail gas enters the secondary air, the tail gas after the tail gas is treated by the equipment, the tail gas is fed into the dilute sulfuric acid concentration of the equipment 23, the dilute sulfuric acid removal equipment, the tail gas concentration of the tail gas after the tail gas is filtered by the equipment 23, the tail gas concentration of the tail gas after the tail gas is treated by the tail gas after the tail gas is filtered, the tail gas is cooled by the tail gas concentration of.
Example 1
Treating a certain dye waste acid for 5 t/h at the normal temperature of 25 ℃, wherein the mass concentration of sulfuric acid in the waste acid is 30%, the mass concentration of organic impurities is 10%, and the balance is water. The purified dilute sulfuric acid is 0.5 t/h, the normal temperature is 25 ℃, and the mass concentration of the dilute sulfuric acid is 10 percent. The fuel is natural gas, and the combustion air is preheated air at 400 ℃. Dilute waste acid enters a spray concentration tower for 5.5 t/h, wherein the mass concentration of sulfuric acid is 28%, the mass concentration of organic impurities is 9%, the rest 63% is water, and the temperature is 25 ℃. The temperature of furnace gas entering a spray concentration tower decomposing furnace is 400 ℃, and the flow rate is 30000 m3H is used as the reference value. The mass concentration of waste acid at the outlet of the spray concentration tower is 75 percent, the flow rate is 2.1 t/h, the waste acid and preheated air with the temperature of 400 ℃ and a proper amount of natural gas fuel enter equipment 6 for incineration, the incineration temperature is controlled to be 1100 ℃, and furnace gas at the outlet of the equipment 6The oxygen concentration was 2%. Outlet furnace gas flow rate 35000 m3And/h, cooling to 200 ℃, entering the equipment 13, and purifying, drying, converting and absorbing to produce an industrial sulfuric acid product with the mass concentration of 98%.
Example 2
Treating the diluted waste sulfuric acid of certain methyl methacrylate for 4 t/h at the normal temperature of 25 ℃, wherein the mass concentration of sulfuric acid in the waste acid is 40%, the mass concentration of ammonium sulfate is 35%, and the balance is water. Purifying dilute sulfuric acid at normal temperature of 25 deg.c for 1 t/h and dilute sulfuric acid mass concentration of 10%. The fuel is natural gas, and the combustion air is preheated air at 400 ℃. Dilute waste acid enters a spray concentration tower for 5.0 t/h, wherein the mass concentration of sulfuric acid is 34 percent, ammonium sulfate is 28 percent, the rest 38 percent is water, and the temperature is 25 ℃. The temperature of furnace gas entering a spray concentration tower decomposing furnace is 450 ℃, and the flow rate is 20000 m3H is used as the reference value. The mass concentration of waste acid at the outlet of the spray concentration tower is 55 percent, the flow rate is 3.1 t/h, the waste acid and preheated air with the temperature of 400 ℃ and a proper amount of natural gas fuel enter equipment 6 to be incinerated, the incineration temperature is controlled to be 1200 ℃, and the oxygen concentration of furnace gas at the outlet of the equipment 6 is 2 percent. Outlet furnace gas flow 24000 m3And/h, cooling to 250 ℃, entering the equipment 13, and purifying, drying, converting and absorbing to produce an industrial sulfuric acid product with the mass concentration of 98%.
Example 3
Treating 10 t/h of certain regenerated lead dilute waste sulfuric acid at the normal temperature of 25 ℃, wherein the mass concentration of sulfuric acid in the waste acid is 40%, the mass concentration of inorganic impurities is 10%, and the balance is water. 2 t/h of purified dilute sulfuric acid, 25 ℃ of normal temperature and 10 percent of dilute sulfuric acid mass concentration. The fuel is natural gas, and the combustion air is preheated air at 500 ℃. The waste acid enters a spray concentration tower for diluting for 12 t/h, wherein the mass concentration of sulfuric acid is 35%, the mass concentration of inorganic impurities is 8.3%, the rest 56.7% is water, and the temperature is 25 ℃. The temperature of furnace gas entering a spray concentration tower decomposing furnace is 500 ℃, and the flow rate is 60000 m3H is used as the reference value. The mass concentration of waste acid at the outlet of the spray concentration tower is 80%, the flow rate is 5.2 t/h, the waste acid and preheated air with the temperature of 500 ℃ and a proper amount of natural gas fuel enter equipment 6 to be incinerated, the incineration temperature is controlled to be 1200 ℃, and the oxygen concentration of furnace gas at the outlet of the equipment 6 is 2%. Outlet furnace gas flow 70000 m3And/h, cooling to 250 ℃, entering the equipment 13, and purifying, drying, converting and absorbing to produce an industrial sulfuric acid product with the mass concentration of 98%.
Example 4
Treating a certain titanium white dilute waste sulfuric acid for 10 t/h at normal temperature25 ℃, the mass concentration of sulfuric acid in the waste acid is 25%, ferrous sulfate is 8%, other inorganic impurities are 2%, and the balance is water. 2 t/h of purified dilute sulfuric acid, 25 ℃ of normal temperature and 5 percent of dilute sulfuric acid mass concentration. The fuel is natural gas, and the combustion air is preheated air at 500 ℃. The waste acid enters a spray concentration tower for diluting for 12 t/h, wherein the mass concentration of sulfuric acid is 21.7 percent, the mass concentration of inorganic impurities is 8.3 percent, the rest 70 percent is water, and the temperature is 25 ℃ at normal temperature. The temperature of furnace gas entering a spray concentration tower decomposing furnace is 500 ℃, and the flow rate is 70000 m3H is used as the reference value. The mass concentration of waste acid at the outlet of the spray concentration tower is 81 percent, the flow rate is 3.2 t/h, the waste acid and preheated air with the temperature of 500 ℃ and a proper amount of natural gas fuel enter equipment 6 to be incinerated, the incineration temperature is controlled to be 1100 ℃, and the oxygen concentration of furnace gas at the outlet of the equipment 6 is 2 percent. Outlet furnace gas flow 83000 m3And/h, cooling to 250 ℃, entering the equipment 13, and purifying, drying, converting and absorbing to produce an industrial sulfuric acid product with the mass concentration of 98%.
Example 5
Treating dilute waste sulfuric acid of certain fine chemical industry for 2 t/h, wherein the mass concentration of sulfuric acid in the waste acid is 20%, the mass concentration of organic impurities is 10%, and the balance is water. 0.5 t/h of purified dilute sulfuric acid, 25 ℃ of normal temperature and 10 percent of dilute sulfuric acid mass concentration. The fuel is natural gas, and the combustion air is preheated air at 300 ℃. Dilute waste acid enters a spray concentration tower for 2.5 t/h, wherein the mass concentration of sulfuric acid is 18%, the mass concentration of organic impurities is 8%, and the rest 74% is water, and the temperature is 25 ℃. The temperature of furnace gas entering a spray concentration tower decomposing furnace is 500 ℃, and the flow rate is 15000 m3H is used as the reference value. The mass concentration of waste acid at the outlet of the spray concentration tower is 75 percent, the flow rate is 0.6 t/h, the waste acid and preheated air with the temperature of 300 ℃ and a proper amount of natural gas fuel enter equipment 6 to be incinerated, the incineration temperature is controlled to be 1100 ℃, and the oxygen concentration of furnace gas at the outlet of the equipment 6 is 2 percent. Outlet furnace gas flow 17000 m3And/h, cooling to 200 ℃, entering the equipment 13, and purifying, drying, converting and absorbing to produce an industrial sulfuric acid product with the mass concentration of 98%.
Claims (10)
1. A process for preparing sulfuric acid by regenerating low-concentration dilute waste sulfuric acid is characterized in that a dilute waste acid spray concentration process using decomposing furnace gas as a concentration heat source is adopted, the low-concentration dilute waste sulfuric acid and dilute sulfuric acid generated in an acid preparation purification process are concentrated and concentrated by controlling the gas-liquid ratio of a spray concentration tower, the concentrated waste sulfuric acid after concentration is sent into a decomposing furnace, and gas discharged from the spray concentration tower is merged into the furnace gas at the outlet of an air preheater; the concentrated waste sulfuric acid is thermally decomposed into high-temperature furnace gas containing sulfur dioxide, sulfur trioxide, water, oxygen, nitrogen, carbon dioxide and other impurities by mixing combustion with preheated combustion-supporting air and fuel in a decomposing furnace, the high-temperature furnace gas recovers heat energy through a waste heat boiler and an air preheater to generate steam, the furnace gas of the decomposing furnace from the waste heat boiler is divided into two paths, one path of the furnace gas is sent to a spray concentration system, the other path of the furnace gas enters the air preheater to preheat air, the furnace gas at the outlet of the air preheater sequentially enters a dilute acid cleaning and purifying process, a dry absorption process and a conversion process to prepare acid to generate an industrial sulfuric acid product with the mass concentration of 98%, the acid preparation tail gas is sent to a desulfurizing tower, the sulfur dioxide and nitrogen oxides in the tail gas are removed by adopting an oxidation method desulfurization and denitrification process, the gas at the outlet of the desulfurizing tower.
2. The process for preparing sulfuric acid from low-concentration dilute waste sulfuric acid as claimed in claim 1, wherein the temperature of the furnace gas of the decomposing furnace is 400 ℃ and ~ 500 ℃ respectively.
3. The process for preparing sulfuric acid from low-concentration waste sulfuric acid as claimed in claim 1, wherein a gas-liquid countercurrent spray concentration process using furnace gas of the pyrolysis furnace as a heat source is adopted, and the gas-liquid ratio of a spray concentration tower is controlled to concentrate industrial waste sulfuric acid containing organic and inorganic substances with a mass concentration of less than 50% to a mass concentration of more than 80%.
4. The process for preparing sulfuric acid from low-concentration waste sulfuric acid as claimed in claim 1, wherein the concentrated waste sulfuric acid with a mass concentration of more than 80% discharged from the spray concentration tower is subjected to solid-liquid separation to remove inorganic impurities in the concentrated waste sulfuric acid and then sent to the decomposing furnace for treatment, the gas discharged from the spray concentration tower is subjected to gas-liquid separation, a part of the gas is returned to the spray concentration tower for adjusting the inlet gas temperature, and a part of the gas is merged into the outlet gas of the air preheater for preparing acid.
5. The process for preparing sulfuric acid from low-concentration diluted waste sulfuric acid as claimed in claim 1, wherein the atomized concentrated waste sulfuric acid with a mass concentration of more than 80%, combustion air at 300 ~ 500 ℃ and auxiliary fuel are injected into the decomposing furnace, the temperature of the decomposing furnace is controlled at 1000 ~ 1200 ℃, the decomposing furnace is operated under a micro-negative pressure, and the oxygen volume concentration of furnace gas at the outlet of the decomposing furnace is 1% ~ 3%.
6. The process for preparing sulfuric acid from low-concentration dilute waste sulfuric acid as claimed in claim 5, wherein the auxiliary fuel is one or more of natural gas, liquefied petroleum gas, coke oven gas, water gas, sulfur and hydrogen sulfide.
7. The process for preparing sulfuric acid from low-concentration waste sulfuric acid by regeneration as claimed in claim 1, wherein the decomposing furnace is a horizontal or vertical structure with a steel shell lining and refractory bricks, secondary air is provided in the decomposing furnace, and an ash discharge system is provided at the tail end.
8. The process for preparing sulfuric acid from low-concentration waste sulfuric acid by regeneration as claimed in claim 1, wherein the acid preparing system adopts twice-conversion and twice-absorption contact method, the diluted acid cleaning process adopts diluted sulfuric acid washing for dust removal, the produced diluted sulfuric acid with mass concentration of 5% ~ 15% is subjected to solid-liquid separation, and then the diluted sulfuric acid is sent to a spray concentration tower for concentration treatment, so that no acidic wastewater is produced in the acid preparing system.
9. The process for preparing sulfuric acid from low-concentration dilute waste sulfuric acid as claimed in claim 1, wherein the waste heat of the high-temperature furnace gas at the outlet of the decomposing furnace and the high-temperature converted gas in the converting step is recovered by a waste heat boiler and an air preheater to produce steam and heated air, and the low-concentration dilute waste sulfuric acid is concentrated by the waste heat of the acid making system.
10. The process for preparing sulfuric acid from low-concentration dilute waste sulfuric acid as claimed in claim 1, wherein the tail gas from acid production is treated by a desulfurization and denitrification process using hydrogen peroxide oxidation, most of the 20% ~ 40% dilute sulfuric acid from the desulfurization tower with mass concentration is returned to the dry absorption process for recycling of make-up water, and a small part of the dilute sulfuric acid is sent to the spray concentration tower for concentration, and the gas from the desulfurization tower is sent to an electric demister for further demisting sulfuric acid mist, and then sent to a chimney for evacuation.
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| CN112815353A (en) * | 2021-01-12 | 2021-05-18 | 桂林理工大学 | Industrial furnace combustion air supply system and control method thereof |
| CN116216753A (en) * | 2023-02-15 | 2023-06-06 | 湖南兴镁源科技股份有限公司 | By Na 2 S 2 O 5 SO produced in the production process 3 SO and SO 2 Preparation of MgSO from waste liquid 4 •7H 2 O method |
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| CN1376633A (en) * | 2002-05-09 | 2002-10-30 | 四川龙蟒集团有限责任公司 | Process for concentrating diluted sulfuric acid and removing impurities |
| US20100233069A1 (en) * | 2006-06-21 | 2010-09-16 | Qvf Engineering Gmbh | Method and system for concentrating waste sulphuric acids from nitration processes |
| CN102050430A (en) * | 2009-11-09 | 2011-05-11 | 中国石油化工股份有限公司 | Method for preparing high concentration sulfuric acid by cracking low concentration sulfuric acid |
| CN103626136A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Wet method used for preparing sulfuric acid from exhaust gas containing hydrogen sulfide |
| CN103552992A (en) * | 2013-10-30 | 2014-02-05 | 中石化南京工程有限公司 | System and method for preparing acid by using sulfur-containing wastewater through dry method |
| CN105480953A (en) * | 2014-10-09 | 2016-04-13 | 中国石油化工股份有限公司 | Alkylated waste acid cracking technology adopting sulphur as fuel |
| CN106554001A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工集团公司 | A kind of acid-making process of comprehensive utilization hydrogen sulfide waste gas and Waste Sulfuric Acid |
| 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 |
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| CN112815353A (en) * | 2021-01-12 | 2021-05-18 | 桂林理工大学 | Industrial furnace combustion air supply system and control method thereof |
| CN116216753A (en) * | 2023-02-15 | 2023-06-06 | 湖南兴镁源科技股份有限公司 | By Na 2 S 2 O 5 SO produced in the production process 3 SO and SO 2 Preparation of MgSO from waste liquid 4 •7H 2 O method |
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