CN112142013B - Method for producing food additive sulfuric acid by nonferrous smelting flue gas - Google Patents
Method for producing food additive sulfuric acid by nonferrous smelting flue gas Download PDFInfo
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- CN112142013B CN112142013B CN202011029927.XA CN202011029927A CN112142013B CN 112142013 B CN112142013 B CN 112142013B CN 202011029927 A CN202011029927 A CN 202011029927A CN 112142013 B CN112142013 B CN 112142013B
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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
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
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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
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- 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
Abstract
The invention discloses a method for producing food additive sulfuric acid by nonferrous smelting flue gas, belonging to the field of food additiveThe technical field of sulfuric acid production, specifically comprises the following steps: the flue gas containing sulfur dioxide from the smelting furnace is subjected to washing, cooling, dedusting and demisting, the flue gas enters a drying tower to be fully contacted with concentrated sulfuric acid, the moisture of the flue gas is removed, and the purified flue gas enters a conversion system to be converted twice, SO that SO is achieved 2 Conversion to SO 3 Converted SO 3 The gas enters an absorption tower to be fully contacted with 98% concentrated sulfuric acid, and a 92.5% or 98% sulfuric acid finished product is produced through process adjustment; the 92.5 percent or 98 percent concentrated sulfuric acid of the product enters a desorption tower to fully remove the reducibility and NO in the acid X And (5) producing the food additive sulfuric acid with different concentrations by waiting for impurities. The method for producing the food additive sulfuric acid uses nonferrous smelting flue gas as a raw material, and improves and perfects the existing technology to produce the food additive sulfuric acid, so that the application range of the nonferrous smelting flue gas is widened, and the method has certain potential benefits.
Description
Technical Field
The invention relates to a method for producing food additive sulfuric acid by nonferrous smelting flue gas, belonging to the technical field of food additive sulfuric acid production.
Background
The food additive sulfuric acid is colorless oily transparent liquid, and hasIs oxidative and corrosive and is soluble in water or ethanol. The food additive sulfuric acid is generally used as a processing aid, such as beer processing, starch processing, dairy processing, fermentation processes, and also has a washing effect on food tools or equipment. The non-ferrous smelting flue gas is a byproduct in the smelting industry, and the main component is SO 2 Because the flue gas contains various impurities and nitrogen oxides, the flue gas is usually only used for producing industrial grade sulfuric acid, and the cost for producing industrial grade sulfuric acid by nonferrous smelting enterprises is high, but the application is limited, the price is low, and the sales is difficult. The existing domestic and foreign food and medical sulfuric acid markets have larger sulfuric acid requirements on food additives, stricter product quality requirements and higher economic value of the food additives, and greatly expand the sulfuric acid sales markets of enterprises. At present, enterprises producing flue gas in the nonferrous smelting industry can only produce industrial grade sulfuric acid, so that the production of food additive sulfuric acid by using nonferrous smelting flue gas has certain social and economic benefits.
Disclosure of Invention
The invention provides a method for producing food additive sulfuric acid by nonferrous smelting flue gas, which finally produces concentrated sulfuric acid products with different concentrations meeting the quality requirements of the food additive and widens the application range of the nonferrous smelting flue gas.
The technical scheme adopted for solving the technical problems is as follows: a method for producing food additive sulfuric acid by nonferrous smelting flue gas, which comprises the following steps:
(1) Purifying: the flue gas with the temperature of about 1200 ℃ is produced by the smelting furnace, and after passing through the waste heat boiler and electric dust collection, the flue gas enters the purification treatment at the temperature of about 300 ℃. The gas-liquid reverse direction fully contacts with the washing, cooling and dedusting through a primary dynamic wave washer and circulating pump equipment, and the technical indexes are controlled: spray acid quantity 1500m 3 About/h, circulating acid concentration of 8-10%, circulating liquid temperature of 55-70 ℃, periodically opening part of dilute acid, maintaining the process index of circulating acid, reducing the flue gas temperature to below 70 ℃ and flue gas dust of less than or equal to 3mg/Nm 3 、Cl≦5PPm、F≦2mg/Nm 3 、As≦2mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the Circulating liquid is introduced into circulating water through a plate heat exchanger to remove heat through a gas cooling tower and a circulating pump, and gas and liquid in the gas cooling tower reversely pass through a packing layer to be chargedWashing and cooling in a separated contact mode, and controlling indexes: circulating acid concentration is 6-8%, circulating liquid temperature is 35-40 ℃, the excessive liquid flows into a primary dynamic wave scrubber, the process index of the circulating acid is maintained, the flue gas temperature is further controlled below 40 ℃, the water inlet temperature of the plate heat exchanger is controlled at 25-28 ℃, and the water outlet temperature is controlled at 33-38 ℃; through a secondary dynamic wave scrubber and circulating pump equipment, gas-liquid reverse full contact scrubbing, cooling and dedusting, and control indexes: circulating acid concentration of 4-6%, F - The temperature of the circulating liquid is less than or equal to 100PPm and 35-37 ℃, the excessive liquid is connected into a gas cooling tower, the process index of circulating acid is maintained, the temperature of the flue gas is reduced to below 37 ℃, and the dust content is less than or equal to 2mg/Nm 3 、Cl≦5PPm、F≦1mg/Nm 3 、As≦1mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the The wet flue gas from the gas cooling tower after cooling and dedusting has reduced temperature, and the dust, fluorine, arsenic, sulfur dioxide and other impurities are removed to meet the requirements, but the acid mist is large in water content, so that the demisting operation is performed by the electric demister. Under the action of a high-voltage current electric field of the rectifier unit, gas enters from the bottom and goes out from the upper part, the anode is a conductive glass steel tube, the cathode is a lead wire, the gas is ionized, acid mist particles with negative charges are obtained, the acid mist particles move to the anode tube of the tube wall under the action of the electric field, the charges are transferred to the anode to lose the electrical property, and then the tube wall is converged and falls down, so that the acid mist is removed, and meanwhile, the harmful impurities such as fine dust, fluorine and arsenic are removed. The primary electric demister controls the secondary voltage to 55KV, the secondary current to 200-400mA, the outlet acid mist to be below 0.03g/Nm3, the secondary electric demister controls the secondary voltage to 55-60KV, the secondary current to 300-500mA, and the outlet acid mist to be below 0.005g/Nm 3; o is adjusted by adjusting the opening of the dilution air valve 2 The mass fraction is controlled at 14.3 percent, SO 2 The mass fraction is controlled at 12.6%. Controlling SO 2 Blower outlet W (O) 2 ):W(SO 2 ) =1.1-1.3:1. Meanwhile, the waste acid with certain acidity and impurities after washing is periodically subjected to open-circuit further treatment and recycling.
(2) And (3) drying: the main equipment comprises: the device comprises a drying tower, a circulating tank, a circulating pump and an anode protector; the concentrated sulfuric acid is utilized to have the characteristic of water absorption, and the main control is as follows: the flue gas after cooling, dedusting and demisting enters a drying tower, gas and liquid are in reverse full contact in a filler layer, the acid concentration of the drying acid is controlled to be 93.5-95%, the temperature of the circulating acid on the tower is controlled to be below 40 ℃, the temperature of the flue gas discharged from the tower is controlled to be below 40 ℃, and finally the moisture of the flue gas is controlled to be less than 0.1g/Nm < 3 >.
(3) Conversion: SO is carried out on the flue gas after drying and purifying 2 The centrifugal fan controls the negative pressure at the inlet of the fan to be not more than-10 KPa, the positive pressure at the outlet to be not more than 40 KPa, and controls the air quantity to be 150000-170000Nm through the inlet guide vane 3 And/h, sending the mixture into a conversion system, and after twice conversion, carrying out SO (sulfur dioxide) 2 The conversion rate reaches more than 99.95 percent. The main equipment comprises: a sulfur dioxide centrifugal fan, a converter (vanadium catalyst is filled in the converter, refractory porcelain balls), a heat exchanger and a heat pipe boiler; the main reaction: SO (SO) 2 +O 2 = SO 3 +q; the specific control is as follows: controlling the concentration of SO2 converted to be about 13%, controlling the temperature of a layer of flue gas inlet passing through the converter to be 390-400 ℃ and controlling the temperature of a catalyst to be 590-630 ℃; the temperature of the inlet of the second layer flue gas of the converter is controlled at 440-450 ℃ and the temperature of the catalyst is controlled at 490-530 ℃; the temperature of the three-layer flue gas inlet of the converter is controlled at 440-450 ℃, the temperature of the catalyst is controlled at 455-475 ℃, the primary conversion is completed, the conversion rate is controlled to be more than 95%, the temperature of the flue gas is controlled to be 180-240 ℃ through a heat pipe boiler, and the flue gas enters a suction tower for absorption; the temperature of the flue gas from the first absorption tower is controlled to be 420-425 ℃ through the inlet of the four layers of flue gas of the converter, and the temperature of the catalyst is controlled to be 430-446 ℃; the five layers of flue gas are converted, the inlet temperature of the flue gas is controlled at 415-416 ℃, the catalyst temperature is controlled at 416-417 ℃, the temperature of the flue gas is controlled between 180-240 ℃ through a heat exchanger, and the flue gas enters a secondary absorption tower for absorption, so that secondary conversion is completed, and the total conversion rate is controlled to be more than 99.95%. The upper part of the conversion layer is a Vk59 type cesium catalyst, the lower part of the conversion layer is a Vk38 vanadium catalyst, the conversion layer is a two-layer Vk38 vanadium catalyst, the conversion layer is a three-layer Vk48 vanadium catalyst, the conversion layer is a four-layer Vk38 vanadium catalyst, and the conversion layer is a five-layer Vk38 vanadium catalyst.
(4) Absorption: SO formed after two conversions 3 Then absorbed twice; the reaction is mainly controlled: SO (SO) 3 +H 2 O=H 2 SO 4 +q; the main equipment comprises: one suction tower, two suction towers, a circulating tank, a circulating pump and an anode protectorA protector. The flue gas after primary conversion enters a suction tower, gas and liquid are fully contacted and absorbed in the reverse direction in the packing layer, the concentration of circulating acid is controlled to be 98-98.8% by adding water in a circulating tank, the temperature of the circulating acid on the tower is controlled to be about 75 ℃, the temperature of the flue gas entering the tower is controlled to be 180-240 ℃, the temperature of the flue gas exiting the tower is controlled to be about 65 ℃, and the redundant heat generated by adding water into the circulating acid is taken away by circulating water of an anode protector; the flue gas after secondary conversion enters a secondary absorption tower, gas and liquid are fully contacted and absorbed in the reverse direction in the filler layer, the concentration of circulating acid is controlled to 98-98.8% by adding water in a circulating tank, the temperature of the circulating acid on the tower is controlled to be 75 ℃, the temperature of the flue gas entering the tower is controlled to be 180-240 ℃, the temperature of the flue gas exiting the tower is controlled to be about 65 ℃, and the redundant heat generated by adding water into the circulating acid is taken away by circulating water of an anode protector; the concentration of the first suction and the second suction is controlled to 98-98.8%, the drying can be carried out to cross acid with the first suction and the second suction, and the acid concentration can be regulated and controlled by adding water, so that 92.5% and 98% sulfuric acid products with certain concentration can be produced.
(5) Desorption: the finished acid is required to be subjected to desorption treatment through a desorption tower, a packing tower and a circulating tank, and the main equipment is as follows: the device comprises a desorption tower, a blower, a packed tower, a circulating tank, a circulating pump, an underground metering tank and an anode protector. The main reaction: SO (SO) 3 +H 2 O=H 2 SO 4 +q; the control index is specifically as follows: producing 98% concentration sulfuric acid, separating the sulfuric acid into one path through an acid pipeline of an upper absorption tower, controlling certain flow through an automatic valve, entering a desorption tower, blowing air into the bottom, reversely and fully contacting gas and liquid in a packing layer, and removing reducibility and NO in the acid X The impurities are removed, the quality requirements of 98% concentration food additives are produced by controlling the concentration of the circulating acid to be 98-98.8% and the temperature of the circulating acid to be about 75 ℃ and the output acid enters a underground metering tank; producing 92.5% concentration sulfuric acid, introducing into circulating tank via acid production via absorption, controlling the concentration of circulating acid to 93.5-94% by adding water, controlling the temperature of circulating acid to about 45deg.C, reversely and fully contacting liquid sulfuric acid in the filler layer of filler tower via circulating pump, branching the acid pipeline on the filler tower, introducing into desorption tower via automatic valve and controlling certain flow, blowing air into bottom, and filling gas-liquidReverse full contact in the material layer to remove the reducibility and NO in the acid X The impurities are removed, the reduction materials are qualified, the nitrate is less than 0.001%, the concentration of the circulating acid is controlled to be 93-94%, and the surplus heat generated by adding water into the circulating acid is taken away by the circulating water of the anode protector; the acid from the tower enters an underground metering tank to produce 92.5% sulfuric acid with the quality requirement of the food additive, and finally the concentrated sulfuric acid products with different concentrations meeting the quality requirement of the food additive are produced through the process equipment and operation control.
The concentration of the dry acid in the step (2) is controlled to be 93.5-94.5%, and the temperature of the dry acid at the inlet is controlled to be below 40 ℃; the relevant devices for trapping acid are added at the upper parts of the drying tower, the first absorption tower and the second absorption tower, so that nitrososulfuric acid micro suspended particles formed in the flue gas cooling process are collected and independently led out of the trap, and nitrate in the circulating acid is reduced. The method comprises the following steps: the upper layer and the lower layer of the silk screen demister at the upper part of the drying tower are provided with grooves for collecting acid, negative pressure is discharged periodically, the collected acid of the acid receiving cups of the demisters at the upper parts of the first absorption tower and the second absorption tower is independently taken over and led out, and all the acid collected by the catcher is independently led out for centralized treatment and sale.
And (3) the finished acid obtained in the step (5) is subjected to desorption treatment through a desorption tower, a packing tower and a circulating tank, and a certain flow rate is controlled. The main equipment comprises: the device comprises a desorption tower, a blower, a packed tower, a circulating tank, a circulating pump, an underground metering tank and an anode protector. The main reaction: SO (SO) 3 +H 2 O=H 2 SO 4 +q; the control index is specifically as follows: producing 98% concentration sulfuric acid, separating the sulfuric acid into one path through an acid pipeline of an upper absorption tower, controlling certain flow through an automatic valve, entering a desorption tower, blowing air into the bottom, reversely contacting gas and liquid in a packing layer, and removing reducibility and NO in the acid X The impurities are removed, the quality requirements of 98% concentration food additives are produced by controlling the concentration of the circulating acid to be 98-98.8% and the temperature of the circulating acid to be about 75 ℃ and the output acid enters a underground metering tank; producing 93% concentration sulfuric acid, introducing into three-absorption circulation tank by one-absorption acid production, controlling the concentration of the circulating acid to 93.5-94% by adding water, controlling the temperature of the circulating acid to about 45 ℃, and adding liquid sulfuric acid into the packed tower by a circulating pumpThe reverse full contact absorption in the packing layer is realized, the acid pipeline on the packing tower branches one way, the acid pipeline enters the desorption tower through an automatic valve and controls certain flow, air is blown into the bottom of the desorption tower, the gas and the liquid are in reverse contact in the packing layer, the reducing substances and nitrate in the acid are removed, the condition that the reducing substances are qualified, the nitrate is less than 0.001%, the concentration of the circulating acid is controlled to be 93-94%, and the redundant heat generated by adding water into the circulating acid is taken away by circulating water of an anode protector is achieved; the acid from the tower enters an underground metering tank to produce 93% sulfuric acid with the quality requirement of the food additive, and finally concentrated sulfuric acid products with different concentrations meeting the quality requirement of the food additive are produced through the process equipment and operation control.
The method for producing the food additive sulfuric acid by using the nonferrous smelting flue gas has the advantages that the pollution discharge amount of the purified waste acid is controlled within a certain range, the primary dynamic wave acid concentration is controlled to be 8-10%, and the secondary dynamic wave acid concentration is controlled to be 4-6%.
The step (1) is purifying: the purification section mainly adopts a first-stage power wave, a gas cooling tower and a second-stage power wave for high-efficiency washing, and mainly aims to remove smoke impurities, cool the smoke impurities, add water glass to control the concentration of fluoride ions below 50mg/L, and remove acid mist from the purified smoke through two-stage electric defogging.
And (3) drying in the step (2): the flue gas after acid mist removal controls the oxygen-sulfur ratio and SO by adjusting a dilution air valve 2 Blower outlet W (O) 2 ):W(SO 2 ) The ratio of the smoke to the water is controlled to be less than 0.1g/Nm, wherein the ratio of the smoke to the water is controlled to be 1.1-1.3:1, and the smoke enters a drying tower for drying 3 The following is given.
The step (3) of conversion: the dried flue gas enters a conversion section for conversion, and SO is carried out 2 Conversion to SO 3 The converter mainly comprises five layers, specifically comprises two conversion steps, and the temperature is controlled through heat exchange of a heat exchanger. The temperature of a layer of flue gas inlet of the converter is controlled to be 390-400 ℃ and the temperature of the catalyst is controlled to be 590-630 ℃; the temperature of the inlet of the second layer flue gas of the converter is controlled at 440-450 ℃ and the temperature of the catalyst is controlled at 490-530 ℃; the temperature of the three-layer flue gas inlet of the converter is controlled at 440-450 ℃ and the temperature of the catalyst is controlled at 455-475 ℃; the temperature of the four layers of flue gas inlets of the converter is controlled to be 420-425 ℃ and the temperature of the catalyst is controlled to be 430-446 ℃; the inlet temperature of five layers of flue gas for conversion is controlled to be 415-416 ℃, and the temperature of the catalyst is controlled to be 416-417 ℃.
And (3) converting a Vk59 cesium catalyst layer at the upper part, a Vk38 vanadium catalyst layer at the lower part, a Vk38 vanadium catalyst layer at the two layers, a Vk48 vanadium catalyst layer at the three layers, a Vk38 vanadium catalyst layer at the four layers, and a Vk38 vanadium catalyst layer at the five layers.
The step (4) is absorption: the converted flue gas is mainly divided into two sections of absorption, the absorption is mainly divided into primary absorption and secondary absorption, the acid concentration is controlled to be 98-98.8%, the converted flue gas is mainly absorbed in a primary absorption tower, and the secondary converted flue gas is absorbed in a secondary absorption tower; the acid can be mutually mixed in the circulation tanks of drying, primary absorption and secondary absorption, and the primary absorption and secondary absorption can maintain the acid concentration balance by adding water.
The step (5) is desorption: the finished acid must be desorbed through a specific tower tank and controlled with a certain flow rate. The main equipment comprises: the device comprises a desorption tower, a blower, a packed tower, a circulating tank, a circulating pump, an underground metering tank and an anode protector. The main reaction: SO (SO) 3 +H 2 O=H 2 SO 4 +q; the control index is specifically as follows: producing 98% concentration sulfuric acid, separating the sulfuric acid into one path through an acid pipeline of an upper absorption tower, controlling certain flow through an automatic valve, entering a desorption tower, blowing air into the bottom, reversely contacting gas and liquid in a packing layer, and removing reducibility and NO in the acid X The impurities are removed, the quality requirements of 98% concentration food additives are produced by controlling the concentration of the circulating acid to be 98-98.8% and the temperature of the circulating acid to be about 75 ℃ and the output acid enters a underground metering tank; producing 93% concentration sulfuric acid, introducing into a circulating tank through acid production by one absorption, controlling the concentration of the circulating acid to 93.5-94% by adding water, controlling the temperature of the circulating acid to about 45 ℃, reversely and fully contacting the liquid sulfuric acid in a packing layer of a packing tower through a circulating pump, branching one way of an acid pipeline on the packing tower, introducing into a desorption tower through an automatic valve and controlling a certain flow, blowing air at the bottom, reversely contacting gas and liquid in the packing layer, and removing reducibility and NO in the acid X And (3) waiting for impurities, achieving qualified reducing substances, less than 0.001% of nitrate, controlling the concentration of the circulating acid to be 93-94%, and adding the circulating acidThe redundant heat generated by the water is taken away by the circulating water of the anode protector; the acid from the tower enters an underground metering tank to produce 93% sulfuric acid with the quality requirement of the food additive, and finally concentrated sulfuric acid products with different concentrations meeting the quality requirement of the food additive are produced through the process equipment and operation control.
The beneficial effects of the invention are as follows: the invention solves the problem that the nonferrous smelting flue gas can not normally produce the food additive sulfuric acid, develops the application channel of the nonferrous smelting flue gas, and has certain social benefit and economic benefit. The method increases the food grade varieties from single varieties for the sulfuric acid of enterprises, expands the market competition channel, radically and thoroughly solves the passive situation that the system reduces or stops production due to the increase of single stock of the products of the enterprises, and has huge potential economic benefit.
Drawings
Fig. 1 is a production flow chart of the present invention.
Detailed Description
The invention will be described in detail with reference to the drawings and the detailed description.
A method for producing food additive sulfuric acid by nonferrous smelting flue gas comprises the following specific implementation steps:
(1) Purifying: the flue gas with the temperature of about 1200 ℃ is produced by the smelting furnace, and after passing through the waste heat boiler and electric dust collection, the flue gas enters the purification treatment at the temperature of about 300 ℃. The gas-liquid reverse direction fully contacts with the washing, cooling and dedusting through a primary dynamic wave washer and circulating pump equipment, and the technical indexes are controlled: spray acid quantity 1500m 3 About/h, circulating acid concentration of 8-10%, circulating liquid temperature of 55-70 ℃, periodically opening part of dilute acid, maintaining the process index of circulating acid, reducing the flue gas temperature to below 70 ℃ and flue gas dust of less than or equal to 3mg/Nm 3 、Cl≦5PPm、F≦2mg/Nm 3 、As≦2mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the Circulating liquid is introduced into circulating water through a plate heat exchanger to remove heat through a gas cooling tower and a circulating pump, and gas and liquid in the gas cooling tower reversely pass through a packing layer to be fully contacted, washed and cooled, so that indexes are controlled: circulating acid concentration of 6-8%, circulating liquid temperature of 35-40 deg.C, and circulating acid maintaining processThe index further controls the temperature of the flue gas below 40 ℃, controls the water inlet temperature of the plate heat exchanger to be 25-28 ℃ and the water outlet temperature to be 33-38 ℃; through a secondary dynamic wave scrubber and circulating pump equipment, gas-liquid reverse full contact scrubbing, cooling and dedusting, and control indexes: circulating acid concentration of 4-6%, F - The temperature of the circulating liquid is less than or equal to 100PPm and 35-37 ℃, the excessive liquid is connected into a gas cooling tower, the process index of circulating acid is maintained, the temperature of the flue gas is reduced to below 37 ℃, and the dust content is less than or equal to 2mg/Nm 3 、Cl≦5PPm、F≦1mg/Nm 3 、As≦1mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the The wet flue gas from the gas cooling tower after cooling and dedusting has reduced temperature, and the dust, fluorine, arsenic, sulfur dioxide and other impurities are removed to meet the requirements, but the acid mist is large in water content, so that the demisting operation is performed by the electric demister. Under the action of a high-voltage current electric field of the rectifier unit, gas enters from the bottom and goes out from the upper part, the anode is a conductive glass steel tube, the cathode is a lead wire, the gas is ionized, acid mist particles with negative charges are obtained, the acid mist particles move to the anode tube of the tube wall under the action of the electric field, the charges are transferred to the anode to lose the electrical property, and then the tube wall is converged and falls down, so that the acid mist is removed, and meanwhile, the harmful impurities such as fine dust, fluorine and arsenic are removed. The primary electric demister controls the secondary voltage to 55KV, the secondary current to 200-400mA, the outlet acid mist to be below 0.03g/Nm3, the secondary electric demister controls the secondary voltage to 55-60KV, the secondary current to 300-500mA, and the outlet acid mist to be below 0.005g/Nm 3; o is adjusted by adjusting the opening of the dilution air valve 2 The mass fraction is controlled at 14.3 percent, SO 2 The mass fraction is controlled at 12.6%. Controlling SO 2 Blower outlet W (O) 2 ):W(SO 2 ) =1.1-1.3:1. Meanwhile, the waste acid with certain acidity and impurities after washing is periodically subjected to open-circuit further treatment and recycling.
(2) And (3) drying: the main equipment comprises: the device comprises a drying tower, a circulating tank, a circulating pump and an anode protector; the concentrated sulfuric acid is utilized to have the characteristic of water absorption, and the main control is as follows: the flue gas after cooling, dedusting and demisting enters a drying tower, gas and liquid are in reverse full contact in a filler layer, the acid concentration of the drying acid is controlled to be 93.5-95%, the temperature of the circulating acid on the tower is controlled to be below 40 ℃, the temperature of the flue gas discharged from the tower is controlled to be below 40 ℃, and finally the moisture of the flue gas is controlled to be less than 0.1g/Nm < 3 >.
(3) Conversion: SO is carried out on the flue gas after drying and purifying 2 The centrifugal fan controls the negative pressure at the inlet of the fan to be not more than-10 KPa, the positive pressure at the outlet to be not more than 40 KPa, and controls the air quantity to be 150000-170000Nm through the inlet guide vane 3 And/h, sending the mixture into a conversion system, and after twice conversion, carrying out SO (sulfur dioxide) 2 The conversion rate reaches more than 99.95 percent. The main equipment comprises: a sulfur dioxide centrifugal fan, a converter (vanadium catalyst is filled in the converter, refractory porcelain balls), a heat exchanger and a heat pipe boiler; the main reaction: SO (SO) 2 +O 2 = SO 3 +q; the specific control is as follows: controlling the concentration of SO2 converted to be about 13%, controlling the temperature of a layer of flue gas inlet passing through the converter to be 390-400 ℃ and controlling the temperature of a catalyst to be 590-630 ℃; the temperature of the inlet of the second layer flue gas of the converter is controlled at 440-450 ℃ and the temperature of the catalyst is controlled at 490-530 ℃; the temperature of the three-layer flue gas inlet of the converter is controlled at 440-450 ℃, the temperature of the catalyst is controlled at 455-475 ℃, the primary conversion is completed, the conversion rate is controlled to be more than 95%, the temperature of the flue gas is controlled to be 180-240 ℃ through a heat pipe boiler, and the flue gas enters a suction tower for absorption; the temperature of the flue gas from the first absorption tower is controlled to be 420-425 ℃ through the inlet of the four layers of flue gas of the converter, and the temperature of the catalyst is controlled to be 430-446 ℃; the five layers of flue gas are converted, the inlet temperature of the flue gas is controlled at 415-416 ℃, the catalyst temperature is controlled at 416-417 ℃, the temperature of the flue gas is controlled between 180-240 ℃ through a heat exchanger, and the flue gas enters a secondary absorption tower for absorption, so that secondary conversion is completed, and the total conversion rate is controlled to be more than 99.95%. The upper part of the conversion layer is a Vk59 type cesium catalyst, the lower part of the conversion layer is a Vk38 vanadium catalyst, the conversion layer is a two-layer Vk38 vanadium catalyst, the conversion layer is a three-layer Vk48 vanadium catalyst, the conversion layer is a four-layer Vk38 vanadium catalyst, and the conversion layer is a five-layer Vk38 vanadium catalyst.
(4) Absorption: SO formed after two conversions 3 Then absorbed twice; the reaction is mainly controlled: SO (SO) 3 +H 2 O=H 2 SO 4 +q; the main equipment comprises: the device comprises a first suction tower, a second suction tower, a circulating tank, a circulating pump and an anode protector. The flue gas after primary conversion enters a suction tower, the gas and the liquid are reversely and fully contacted and absorbed in a filler layer, and the concentration of the circulating acid is controlled to be 98-98.8% by adding water in a circulating groove,The temperature of the circulating acid on the tower is controlled to be about 75 ℃, the temperature of the flue gas entering the tower is controlled to be between 180 and 240 ℃, the temperature of the flue gas exiting the tower is controlled to be about 65 ℃, and the redundant heat generated by adding water into the circulating acid is taken away by circulating water of an anode protector; the flue gas after secondary conversion enters a secondary absorption tower, gas and liquid are fully contacted and absorbed in the reverse direction in the filler layer, the concentration of circulating acid is controlled to 98-98.8% by adding water in a circulating tank, the temperature of the circulating acid on the tower is controlled to be 75 ℃, the temperature of the flue gas entering the tower is controlled to be 180-240 ℃, the temperature of the flue gas exiting the tower is controlled to be about 65 ℃, and the redundant heat generated by adding water into the circulating acid is taken away by circulating water of an anode protector; the concentration of the first suction and the second suction is controlled to 98-98.8%, the drying can be carried out to cross acid with the first suction and the second suction, and the acid concentration can be regulated and controlled by adding water, so that 92.5% and 98% sulfuric acid products with certain concentration can be produced.
(5) Desorption: the finished acid is required to be subjected to desorption treatment through a desorption tower, a packing tower and a circulating tank, and the main equipment is as follows: the device comprises a desorption tower, a blower, a packed tower, a circulating tank, a circulating pump, an underground metering tank and an anode protector. The main reaction: SO (SO) 3 +H 2 O=H 2 SO 4 +q; the control index is specifically as follows: producing 98% concentration sulfuric acid, separating the sulfuric acid into one path through an acid pipeline of an upper absorption tower, controlling certain flow through an automatic valve, entering a desorption tower, blowing air into the bottom, reversely and fully contacting gas and liquid in a packing layer, and removing reducibility and NO in the acid X The impurities are removed, the quality requirements of 98% concentration food additives are produced by controlling the concentration of the circulating acid to be 98-98.8% and the temperature of the circulating acid to be about 75 ℃ and the output acid enters a underground metering tank; producing 92.5% concentration sulfuric acid, introducing into a circulating tank through acid production by one absorption, controlling the concentration of the circulating acid to 93.5-94% by adding water, controlling the temperature of the circulating acid to about 45 ℃, reversely and fully contacting the liquid sulfuric acid in a filler layer of a filler tower through a circulating pump, branching one way through an acid pipeline on the filler tower, introducing into a desorption tower through an automatic valve and controlling certain flow, blowing air into the bottom, reversely and fully contacting gas and liquid in the filler layer, and removing reducibility and NO in the acid X And the impurities are removed, the reduction materials are qualified, the nitrate is less than 0.001%, and the concentration of the circulating acid is controlled to 93-94% of the surplus heat generated by adding water to the circulating acid is taken away by the circulating water of the anode protector; the acid from the tower enters an underground metering tank to produce 92.5% sulfuric acid with the quality requirement of the food additive, and finally the concentrated sulfuric acid products with different concentrations meeting the quality requirement of the food additive are produced through the process equipment and operation control.
Claims (2)
1. A method for producing food additive sulfuric acid by nonferrous smelting flue gas, which comprises the following steps:
step 1, purifying: the flue gas with the temperature of 1200 ℃ is produced by a smelting furnace, and after passing through a waste heat boiler and electric dust collection, the flue gas enters purification treatment at the temperature of 300 ℃; the gas-liquid reverse direction fully contacts with the washing, cooling and dedusting through a primary dynamic wave washer and circulating pump equipment, and the technical indexes are controlled: spray acid quantity 1500m 3 And/h, the concentration of the circulating acid is 8-10%, the temperature of the circulating liquid is 55-70 ℃, part of dilute acid is opened periodically, the process index of the circulating acid is maintained, the temperature of the flue gas is reduced to be below 70 ℃, and the flue gas dust is less than or equal to 3mg/Nm 3 、Cl≦5ppm、F≦2mg/Nm 3 、As≦2mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the Circulating liquid is introduced into circulating water through a plate heat exchanger to remove heat through a gas cooling tower and a circulating pump, and gas and liquid in the gas cooling tower reversely pass through a packing layer to be fully contacted, washed and cooled, so that indexes are controlled: circulating acid concentration is 6-8%, circulating liquid temperature is 35-40 ℃, excessive liquid flows into a primary dynamic wave scrubber, the process index of circulating acid is maintained, the flue gas temperature is controlled below 40 ℃, the water inlet temperature of the plate heat exchanger is controlled at 25-28 ℃, and the water outlet temperature is controlled at 33-38 ℃; through a secondary dynamic wave scrubber and circulating pump equipment, gas-liquid reverse full contact scrubbing, cooling and dedusting, and control indexes: circulating acid concentration of 4-6%, F - The temperature of the circulating liquid is less than or equal to 100ppm and 35-37 ℃, the excessive liquid is connected into a gas cooling tower, the process index of the circulating acid is maintained, the temperature of the flue gas is reduced to below 37 ℃, and the dust content is less than or equal to 2mg/Nm 3 、Cl≦5ppm、F≦1mg/Nm 3 、As≦1mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the Adopting an electric demister to carry out demisting operation; under the action of high-voltage current electric field of rectifier unit, gas is introduced from bottom portion and discharged from upper portion, anode is made of conductive glass fibre reinforced plastic pipe, cathode is made of lead wire, and gas is ionized so as to obtain the invented productThe acid mist particles with negative charges are moved to the anode tube of the tube wall under the action of an electric field, the charges are transferred to the anode to lose the electric property, and the charges are collected on the tube wall, so that the acid mist is removed, and harmful impurities are removed together while defogging; the primary electric demister controls the secondary voltage to 55kV, the secondary current to 200-400mA and the outlet acid mist to 0.03g/Nm 3 The secondary voltage is controlled to be 55-60kV, the secondary current is controlled to be 300-500mA, and the outlet acid mist is controlled to be 0.005g/Nm 3 The following are set forth; o is adjusted by adjusting the opening of the dilution air valve 2 The mass fraction is controlled at 14.3 percent, SO 2 The mass fraction is controlled at 12.6%; controlling SO 2 Blower outlet W (O) 2 ):W(SO 2 ) =1.1-1.3:1; meanwhile, the waste acid with certain acidity and impurities after washing is periodically subjected to open-circuit further treatment and recycling;
step 2, drying: the main equipment comprises: the device comprises a drying tower, a circulating tank, a circulating pump and an anode protector; the concentrated sulfuric acid is utilized to have the characteristic of water absorption, and the main control is as follows: the flue gas after cooling, dedusting and demisting enters a drying tower, gas and liquid are in reverse full contact in a filler layer, the acid concentration of the drying acid is controlled to be 93.5-95%, the temperature of a circulating acid upper tower is controlled to be below 40 ℃, the temperature of a flue gas discharged from the tower is controlled to be below 40 ℃, and finally the moisture of the flue gas is controlled to be 0.1g/Nm through mutual stringing of the acid concentration of drying and one absorption 3 The following are set forth;
step 3, conversion: SO is carried out on the flue gas after drying and purifying 2 The centrifugal fan controls the negative pressure of the inlet of the fan to be not more than-10 kPa, the positive pressure of the outlet to be not more than 40 kPa, and controls the air quantity to be 150000-170000Nm through the inlet guide vane 3 And/h, sending the mixture into a conversion system, and after twice conversion, carrying out SO (sulfur dioxide) 2 The conversion rate reaches more than 99.95 percent; the main equipment comprises: sulfur dioxide centrifugal fan, converter, heat exchanger and heat pipe boiler; the main reaction: SO (SO) 2 +O 2 → SO 3 +q; the specific control is as follows: controlling converted SO 2 The concentration is 13%, the temperature of a layer of flue gas inlet passing through the converter is controlled to be 390-400 ℃, and the temperature of the catalyst is controlled to be 590-630 ℃; the temperature of the inlet of the second layer flue gas of the converter is controlled at 440-450 ℃ and the temperature of the catalyst is controlled at 490-530 ℃; three-layer flue gas inlet temperature control of converterThe catalyst is prepared at 440-450 ℃, the catalyst temperature is controlled at 455-475 ℃, the primary conversion is completed, the conversion rate is controlled to be more than 95%, the flue gas temperature is controlled to be 180-240 ℃ through a heat pipe boiler, and the flue gas enters a suction tower for absorption; the temperature of the flue gas from the first absorption tower is controlled to be 420-425 ℃ through the inlet of the four layers of flue gas of the converter, and the temperature of the catalyst is controlled to be 430-446 ℃; the five-layer flue gas inlet temperature is controlled at 415-416 ℃, the catalyst temperature is controlled at 416-417 ℃, the flue gas temperature is controlled at 180-240 ℃ through a heat exchanger, and the flue gas enters a secondary absorption tower for absorption, so that secondary conversion is completed, and the total conversion rate is controlled to be more than 99.95%; converting one layer of cesium catalyst with Vk59 type upper part, one layer of lower part Vk38 vanadium catalyst, two layers of Vk38 vanadium catalyst, three layers of Vk48 vanadium catalyst, four layers of Vk38 vanadium catalyst and five layers of Vk38 vanadium catalyst;
step 4, absorption: SO formed after two conversions 3 Then absorbed twice; the reaction is mainly controlled: SO (SO) 3 +H 2 O=H 2 SO 4 +q; the main equipment comprises: a first suction tower, a second suction tower, a circulating tank, a circulating pump and an anode protector; the flue gas after primary conversion enters a suction tower, gas and liquid are reversely and fully contacted and absorbed in a packing layer, the concentration of circulating acid is controlled to be 98-98.8% by adding water in a circulating tank, the temperature of the circulating acid on the tower is controlled to be 75 ℃, the temperature of the flue gas entering the tower is controlled to be 180-240 ℃, the temperature of the flue gas exiting the tower is controlled to be 65 ℃, and the redundant heat generated by adding water into the circulating acid is taken away by circulating water of an anode protector; the flue gas after secondary conversion enters a secondary absorption tower, gas and liquid are fully contacted and absorbed in the reverse direction in the packing layer, the concentration of circulating acid is controlled to 98-98.8% by adding water in a circulating tank, the temperature of the circulating acid on the tower is controlled to 75 ℃, the temperature of the flue gas entering the tower is controlled to 180-240 ℃, the temperature of the flue gas exiting the tower is controlled to 65 ℃, and the redundant heat generated by adding water into the circulating acid is taken away by circulating water of an anode protector; the concentration of the primary absorption and secondary absorption circulating acid is controlled to be 98-98.8%, the primary absorption and secondary absorption can be used for carrying out mutual acid mixing, and the acid concentration can be regulated and controlled by adding water, so that sulfuric acid products with the concentration of 92.5% and 98% can be produced;
step 5, desorption: the finished acid is required to be subjected to desorption treatment through a desorption tower, a packing tower and a circulating tank, and the main equipment is as follows: desorber, blower, packed tower, circulation tank, circulation pump and groundA lower metering tank and an anode protector; the main reaction: SO (SO) 3 +H 2 O=H 2 SO 4 +Q；
The method is characterized in that:
in the step 2, a trapping acid collecting device is arranged in the drying tower to collect nitrososulfuric acid micro-suspended particles formed in the flue gas cooling process, the micro-suspended particles are independently led out of the trapping device to reduce nitrate in the circulating acid, and the collected condensed acid is independently treated;
in the step 4, a trapping acid collecting device is arranged in the first absorption tower and the second absorption tower, so that nitrososulfuric acid micro suspended particles formed in the flue gas cooling process are collected and independently led out of a trap, nitrate in circulating acid is reduced, and the collected condensing acid is independently treated;
in the step 5, the control indexes are specifically as follows: when 98% concentration sulfuric acid is produced, the sulfuric acid enters the desorption tower through an acid absorption pipeline branch path, an automatic valve and a certain flow rate control, air is blown into the bottom of the desorption tower, and the gas and the liquid are in reverse full contact in the packing layer, so that the reducibility and NO in the acid are removed X Impurities, namely qualified reducing substances, nitrate less than 0.001%, controlling the concentration of the circulating acid to be 98-98.8%, controlling the temperature of the circulating acid to be 75 ℃, and enabling the acid discharged from the tower to enter a subsurface metering tank to produce sulfuric acid with the quality required by 98% concentration of food additives; when producing 92.5% concentration sulfuric acid, the sulfuric acid enters a circulating tank through one absorption to produce acid, the concentration of the circulating acid is controlled to be 93.5-94% and the temperature of the circulating acid is controlled to be 45 ℃, the circulating pump is used for controlling the circulating acid to be in reverse full contact with the liquid sulfuric acid in a packing layer of a packing tower, the acid pipeline branches into one path on the packing tower, the sulfuric acid enters a desorption tower through an automatic valve and a certain flow rate is controlled, the air is blown into the bottom of the desorption tower, the gas and the liquid are in reverse full contact with the packing layer, and the reducibility and NO in the acid are removed X Impurities, namely qualified reducing substances, nitrate less than 0.001%, and controlling the concentration of the circulating acid to be 93-94%, wherein excessive heat generated by adding water into the circulating acid is taken away by circulating water of the anode protector; the acid from the tower enters an underground metering tank to produce 92.5% sulfuric acid with the quality requirement of the food additive, and the concentrated sulfuric acid with different concentrations meeting the quality requirement of the food additive is finally produced by controlling the process equipment and the operationThe product is obtained.
2. A method for producing sulfuric acid as a food additive from nonferrous smelting flue gas according to claim 1, wherein: the sewage discharge amount of the purified sewage acid is controlled to be 350-450m 3 /d。
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