CN1449861A - Method and device for removing sulphur dioxide in flue gas by zinc oxide - Google Patents
Method and device for removing sulphur dioxide in flue gas by zinc oxide Download PDFInfo
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Abstract
The present invention relates to a wet flue gas desulfurizing method for absorbing low-concentration sulfur dioxide flue gas by using material containing zinc oxide. Said invention uses the zinc-oxide contained material which is intemediate product of lead and zinc smelting plant as absorbent, and said method includes the steps of making slurry, absorption, absorptive slag separation and absorptive slag treatment, etc. Said invention adopts turbulent ball absorption tower, its absorption efficiency is high, adopts foamed washing tower to wash the absorbed flue gas with water, then uses double-baffle foam-remover to remove foam, and its foam-removing effect is good, the fan is placed after foam-remover, and in the absorption circulating slurry liquor an oxidation inhibitor is added, so that said solution can be circularly used for a long period.
Description
The invention belongs to a flue gas desulfurization method and a device, in particular to a wet flue gas desulfurization method and a device for absorbing low-concentration sulfur dioxide flue gas by using a material containing zinc oxide.
The background technology of the invention is a zinc oxide absorption method of a Japan Yandao smelting plant, which adopts zinc calcine produced by a zinc concentrate fluidized roaster to be ground and then to be made into slurry with water and dilute sulphuric acid, sulfur dioxide in tail gas of acid making and flue gas of a sintering machine is absorbed by a non-filling absorption tower, the generated absorption slag is subjected to acid decomposition by adding sulphuric acid, high-concentration sulfur dioxide gas is produced for making acid, and zinc sulphate solution is returned to a smelting process flow. The method uses the smelting intermediate product zinc calcine as an absorbent, does not purchase the absorbent, returns to the smelting process flow after the absorption slag is treated, has no problem of foreign sales of absorption byproducts, and recycles the absorbed sulfur dioxide used for preparing acid. However, the method has the disadvantages of long process, more equipment, large investment, and poor equipment blockage and defoaming effects, and is not popularized and applied in industry.
The invention aims to solve the problems and provide a method and a device for removing sulfur dioxide in flue gas by zinc oxide, which have the advantages of simple process, reliable equipment operation, low investment, good implementation effect and no secondary pollution.
The technical steps of the invention are as follows: (1) pulping, (2) absorbing, (3) absorbing and separating pulp, and (4) absorbing and treating slag, and is characterized in that: the concentration of the treated flue gas containing sulfur dioxide is 0.03-3%, and the flue gas temperature is 10-150 ℃ and the flue gas is subjected to dust removal or not subjected to dust removal; the absorbent is a material with a particle size of less than 100 meshes accounting for more than 90% and zinc oxide content of more than 40%, and can be groundThe zinc calcine can also be prepared by directly using zinc smoke dust, the using amount of the zinc calcine is 1.2-1.3 times of the theoretical amount, and the pulping process is directly carried out in an absorption circulating tank; the concentration of the ore pulp is controlled to be 18-22% in the absorption process, and the pH value of an absorption end point is controlled to be 4.5-5.0; adding hydroquinone antioxidant less than 0.1% into the circulating liquid; the absorption tower adopts a turbulent ball tower, the air speed of the hollow tower is 1.5-6.0 m/s, and the spraying density is 20-100 m3/m2H; separating the absorption slag from the solution, and then treating the absorption slag by one of thermal decomposition, acid decomposition and air oxidation; the thermal decomposition temperature is more than 350 ℃; performing acid decomposition by adopting zinc electrolysis waste electrolyte, controlling the decomposition temperature to be 70-90 ℃, and blowing air into decomposition slurry for desorption after the decomposition is finished; the air oxidation method is to prepare 20-25% slurry of the absorption slag in an air oxidation tank 14, wherein an air oxidation blow pipe is distributed at the bottom of the tank, and the center of the tank is provided with an air oxidation blow pipeIt has stirrer, flow guide plate and vortex bubbler installed around the stirrer.
The device for the method for removing the sulfur dioxide in the flue gas by the zinc oxide comprises an absorption tower 1, a demister 3, a fan 4, a chimney 5, a filter press 11 and a filter pump 8, and is characterized in that a washing tower 2 is connected between the absorption tower 1 and the demister 3; the fan 4 is arranged between the demister 3 and the chimney 5; the absorption slurry is directly sent to a filter press 11 by a filter pump 8 for filtering; the washing tower 2 is a foam washing tower; the filter press 11 is a chamber filter press.
The invention has the advantages that no absorbent is needed to be purchased from the lead-zinc smelting plant, and no absorption by-product is produced, compared with the zinc oxide absorption method of the Japan radiant island smelting plant, the invention has the following advantages: the zinc smoke dust produced by the zinc concentrate fluidized bed roaster can be directly added into the absorption circulation tank for pulping without grinding equipment and pulping equipment; the absorption tower adopts a turbulent ball absorption tower, the absorption efficiency is high, and the equipment is not blocked; the smoke coming out of the absorption tower is subjected to foam removal by a secondary blocking foam remover after being washed by water in a foam washing tower, so that the good foam removal effect is achieved, and the fan can stably run for a long time; the fanis arranged behind the demister, so that the system works under negative pressure, and the operating environment is good; adding oxygen inhibitor into the absorption slurry to make ZnSO in the circulating liquid4The concentration is kept at a certain value, so that the solution of the system can be recycled for a long time; absorb the dregsSlag treatment is carried out after filtration, so that soluble harmful elements are reduced and the harmful elements enter a smelting process; three different slag treatment methods are adopted, so that the waste gas treatment and the smelting process are closely combined; the acid treatment method of the slag adopts waste electrolyte, so that the acid in smelting is more easily balanced. The invention has simple flow and equipment, stable and smooth process, less investment, convenient operation, easy mastering of technical conditions and good labor conditions, is tightly combined with the smelting process, and can be widely used for treating low-concentration sulfur dioxide flue gas in the industries of smelting, chemical engineering, sulfuric acid production and the like.
The process flow diagram of the invention is shown in the attached drawing.
Embodiments are described with reference to the accompanying drawings:
the labels in the figures indicate: the device comprises an absorption tower 1, a washing tower 2, a demister 3, a fan 4, a chimney 5, an absorption circulating tank 6, an absorption circulating pump 7, a filter pump 8, a washing circulating tank 9, a washing circulating pump 10, a box-type filter press 11, a fluidized bed roaster 12, an acid decomposition tank 13 and an air oxidation tank 14.
5 kiloton/a electro-zinc engineering of Kunming Yunyi Zinc industry Limited company, for treating low-concentration sulfur dioxide flue gas generated by zinc leaching residue volatilization kiln and defluorination chlorine multi-hearth roasting furnace, the flue gas amount is 42500m3The flue gas contains 3570t/a of sulfur dioxide, the absorption efficiency of the sulfur dioxide is 96-98%, the sulfuric acid is produced by recovering the sulfur dioxide, the treatment cost is 294 yuan/ton of sulfur dioxide, and the investment of project fixed assets is 400 ten thousand yuan (excluding a slag treatment system). The main equipment is as follows:phi 3.2m turbulent ball absorption tower, phi 3.2m foam washing tower, phi 3.0m multiple baffle foam remover, 80m3Absorption circulation tank, 15m3Washing circulation tank, 50m2And (4) boiling the roasting furnace.
The method comprises the following four technical steps:
(1) pulping
The absorption raw materials are the smoke dust of a cyclone dust collector and an electric dust collector produced by a zinc fluidized bed roaster of the company, the absorption raw materials contain zinc oxide of about 60 percent, the granularity is less than 100 meshes and accounts for more than 90 percent, and the consumption is 1.25 times of the theoretical amount, and the absorption raw materials are directly added into an absorption circulation tank 6 for pulping. When the absorbent reaches saturation in the absorption process, a part of absorption serous fluid is discharged to be filtered, and new absorbent and pulping solution (absorption slag filtering solution and washing solution) are added in the absorption circulation tank, wherein the pulp concentration is controlled to be 20% in the pulping process.
(2) Absorption of
The main absorption reaction is:
at the same time, the following side reactions are carried out:
the temperature of the flue gas entering the absorption is 130 ℃, the sulfur dioxide content is 0.49 percent, and the dust content is 0.2g/m3The gas enters a turbulent ball absorption tower 1 to remove sulfur dioxide in the flue gas, and hollow filler pellets placed between sieve plates in the tower are utilized to generate more violent turbulence under the action of the impulsive force of ascending gas flow, the buoyancy and the gravity of liquid, so that the contact area of the gas and the liquid is increased, the mass transfer effect is enhanced, and the empty tower speed in the turbulent ball absorption tower is controlled to be 2.5m/s and the spraying density is controlled to be 40m3/m2H, the absorption efficiency is 96-98%. The absorbed flue gas is washed by water in a foam washing tower 2, and is introduced into a chimney 5 by a fan 4 after a demister 3 is removed again. The absorption liquid of the absorption tower flows into an absorption circulation tank 6 from the tower and then is sent to the absorption tower for recycling by an absorption circulation pump 7, and the washing liquid of the washing tower and the foam remover liquid flow into a washing circulation tank 9 and then are sent to the washing tower for recycling by a washing circulation pump 10.
The generated absorption slag is ZnSO3·2.5H2And O solid, when the pH value of the absorption ore pulp circulating spray is reduced to 4.5, the absorption ore pulp is close to saturation, a part of absorption saturated ore pulp is discharged to be filtered, new absorption slurry is supplemented in the absorption circulating tank, the absorption circulating tank is circularly sprayed, and the absorption circulating tank is continuously stirred to keep the absorption saturated ore pulp in a suspended state.
Due to smokeContains a small amount of sulfur trioxide and a small amount of ZnSO in the absorption process3Oxidized to generate zinc sulfate solution, so that zinc ions are continuously increased in the circulating process, and 0.05 percent of hydroquinone oxygen inhibitor is added into the absorption slurry, so that the concentration of the zinc ions in the circulating solution is kept at a certain value, and the absorption slurry is recycled for a long time.
(3) Separation of absorption pulp
The absorption slag is sent to a filter press 11 from the absorption circulating tank by a filter pump 8 for filtration, and the produced absorption slag contains ZnSO3About 40 percent of the water content is 30 percent, the water content is sent to the absorption slag for treatment, and the filtrate flows into the absorption circulating tank 6 for pulping.
(4) Absorption slag treatment
The absorption slag treatment can be carried out in the following three ways, namely, the thermal decomposition treatment is adopted in the zinc electrolysis engineering of Kunming Yunyi Zinc industry Co.
a. Thermal decomposition treatment
ZnSO3The thermal decomposition of the crystals is carried out by the following steps:
120℃ 200℃ 270℃
the thermal decompositiontemperature is controlled to be more than or equal to 350 ℃, the absorption slag can be thermally decomposed to regenerate zinc oxide, and high-concentration sulfur dioxide gas is produced for acid production. In the embodiment, the absorption slag and the zinc concentrate are mixed and enter the fluidized bed roaster 12 to be thermally decomposed at 850-920 ℃ to produce zinc calcine and zinc smoke dust.
b. Acid decomposition treatment
ZnSO3The acid decomposition of the crystals is carried out as follows:
according to the method, 100-200 g/l zinc electrolysis waste electrolyte containing sulfuric acid is added into filter residues and is carried out in an acid decomposition tank 13, the acid decomposition tank is indirectly heated at 70-90 ℃ for 30 minutes, decomposition time is 5g/l, gas containing 50% of sulfur dioxide is generated by decomposition and used for preparing acid, air is blown into decomposed solution, sulfur dioxide gas in the solution is separated, gas containing more than 5% of sulfur dioxide is separated and used for preparing acid, the decomposition residues and the solution are sent to a zinc smelting and leaching process, and decomposition rate is more than 95%.
c. Air oxidation treatment
ZnSO3The air oxidation of the crystals is carried out as follows:
Claims (7)
1. The method for removing sulfur dioxide in flue gas by using zinc oxide comprises the following technical steps: (1) pulping, (2) absorbing, (3) separating the absorbing pulp, and (4) treating the absorbing slag, wherein the treated flue gas contains 0.03-3% of sulfur dioxide, and is dedusted or not dedusted at the temperature of 10-150 ℃; the used absorbent is a material with the granularity of less than 100 meshes and more than 90 percent and containing more than 40 percent of zinc oxide, can be ground zinc calcine, and can also be directly used zinc smoke dust, the using amount is 1.2 to 1.3 times of the theoretical amount, and the pulping process is directly carried out in the absorption circulating tank (6); the concentration of the ore pulp is controlled to be 18-22% in the absorption process, and the pH value of the absorption end point is controlled to be 4.5-5.0.
2. The process of claim 1 wherein less than 0.1% hydroquinone oxygen barrier is added to the absorption cycle liquid in the absorption step.
3. The method according to claim 1, wherein the absorption tower (1) in the absorption step is a turbulent ball absorption tower, and the air velocity of the turbulent ball absorption tower is 1.5-6.0 m/s, and the spraying density is 20-100 m3/m2·h。
4. The method according to claim 1, wherein the absorption residue is separated from the solution and then treated, wherein one of thermal decomposition, acid decomposition and air oxidation is selected, and wherein: the thermal decomposition temperature is more than 350 ℃; performing acid decomposition by adopting zinc electrolysis waste electrolyte, controlling the decomposition temperature to be 70-90 ℃, and blowing air into decomposition slurry for desorption after the decomposition is finished; the air oxidation method is characterized in that 20-25% of slurry prepared from absorption slag is carried out in an air oxidation tank (14), air oxidation blow pipes are distributed at the bottom of the tank, a stirrer is arranged in the center of the tank, and a guide plate and a vortex bubbler are arranged on the periphery of the tank.
5. The device for removing the sulfur dioxide in the flue gas by the zinc oxide according to claim 1, which comprises an absorption tower (1), a demister (3), a fan (4), a chimney (5), a filter press (11) and a filter pump (8), and is characterized in that a washing tower (2) is connected between the absorption tower (1) and the demister (3), the fan (4) is arranged between the demister (3) and the chimney (5), and the absorption slurry is directly sent to the filter press (11) for filtering by the filter pump (8).
6. The apparatus according to claim 5, characterized in that the scrubber (2) is a foam scrubber.
7. The apparatus according to claim 5, characterized in that the filter press (11) is a chamber filter press.
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