CN110280105B - Method and device for cooperatively treating acid mist by wet desulfurization of acid making tail gas - Google Patents

Method and device for cooperatively treating acid mist by wet desulfurization of acid making tail gas Download PDF

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CN110280105B
CN110280105B CN201910713579.9A CN201910713579A CN110280105B CN 110280105 B CN110280105 B CN 110280105B CN 201910713579 A CN201910713579 A CN 201910713579A CN 110280105 B CN110280105 B CN 110280105B
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absorption
concentration
process water
section
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CN110280105A (en
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曾子平
刘应隆
钱益虎
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Asia Pacific Environmental Protection Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • B01D53/185—Liquid distributors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/38—Removing components of undefined structure
    • B01D53/40—Acidic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a method for cooperatively treating acid mist by wet desulfurization of acid making tail gas, which comprises the following steps: (1) Spraying the tail gas to be treated with an ammonium sulfate solution with the mass percent concentration of less than 35%, performing gas-liquid contact collision, and performing countercurrent contact with an aqueous solution containing ammonium sulfate and ammonium sulfite with the pH value of 2-4 to obtain the tail gas at 20-30 ℃; (2) Then reacts with absorption liquid with pH value of 4-6 to obtain tail gas after tail absorption; the absorption liquid is an aqueous solution containing ammonium sulfate and ammonium sulfite with the mass percentage concentration of 10-25%; (3) The tail gas after tail absorption is sprayed and washed by an ammonium sulfate aqueous solution with the density of 1.02-1.06 kg/L, then sprayed and washed by an ammonium sulfate aqueous solution with the density of less than 1.02kg/L, and then discharged by a demisting device. The invention has the advantages that: the removal rate of acid mist in the tail gas exceeds 90%, and the acid mist is controlled at 25mg/Nm 3 The following are set forth; can also control the sulfur dioxide in the clean tail gas after desulfurization to be 15mg/Nm 3 The following are free NH 3 ≤2mg/Nm 3 。

Description

Method and device for cooperatively treating acid mist by wet desulfurization of acid making tail gas
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method and a device for cooperatively treating acid mist by wet desulfurization of acid making tail gas.
Background
The existing tail gas desulfurization process is mature, but with the continuous deep concept of resource recycling, the acid mist removal requirements are more and more strict. The standard implementation of the ion chromatography (HJ 544-2016) for measuring the sulfuric acid mist of the waste gas of the fixed pollution source improves the detection requirement of the acid mist, and the tail gas containing the acid mist (such as sulfuric acid tail gas and the like) cannot meet the environmental protection requirement through the traditional wet desulfurization. The acid mist detection method is increased compared with the previous detection methodAdding two alkali solution (NaOH or KOH) impact absorption bottles for continuous sampling to increase the acid mist content of partial tail gas by several times than the previous method, wherein the value of the acid mist content is tens of mg/m 3 Increasing to hundreds of mg/m 3 The above increases the acid mist removal requirements.
(HJ 544-2016) sulfuric acid mist definition: "sulfuric acid mist" includes small droplets of sulfuric acid, sulfur trioxide and soluble sulfate in particulate matter. "thus controlling the acid mist content controls both the inlet acid mist and the soluble sulfate salt produced during desulfurization.
The tail gas inlet temperature is typically below the acid dew point temperature. Gaseous SO 3 Or H 2 SO 4 As the tail gas passes through the desulfurization system, the tail gas is rapidly cooled to below the acid dew point at a cooling rate that is greater than that of gaseous SO 3 Or H 2 SO 4 The rate of absorption by the absorbent in the absorber is much faster, SO 3 Or H 2 SO 4 Submicron-sized sulfuric acid mist which is difficult to capture is rapidly formed. Most of the existing tail gas desulfurization devices are built-in concentration and absorption mode and are simple in defogging mode, and cannot meet the environmental protection requirements. The acid mist is removed from the top of the tail absorption tower by using a conventional wet type electric mist eliminator or a fiber mist eliminator. At present, the wet type electric demisting has higher mist drop removal rate but lower acid mist removal rate, the acid mist removal efficiency of the single-stage wet type electric demisting is about 30-60%, and the acid mist removal rate of the single-stage wet type electric demisting is even lower than 30% for acid mist with lower particle size. Because gas-liquid entrainment, water mist drops and the like exist in the tail gas of the wet desulfurization outlet, wet electricity can preferentially remove the water mist and the gas-liquid entrainment, and the removal rate of acid mist is lower. Therefore, the acid-making tail gas generally needs to be provided with a two-stage wet-type electric demister to meet the existing environmental protection requirements, and has the advantages of large investment, large occupied area, high energy consumption and high operation cost; the fiber demister has higher acid mist removal rate for larger particle diameter, but the actual removal rate of the fiber demister is less than a theoretical calculation value affected by other conditions, (HJ 544-2016) is implemented in a standard way, the fiber demister is difficult to discharge up to the standard, the fiber demister has large investment, large occupied area and large resistance (a draught fan can be needed to be improved or a booster fan can be added), and the operation cost is higher.
Disclosure of Invention
The invention aims to provide a method for cooperatively treating acid mist by wet desulfurization of acid making tail gas, which can effectively remove acid mist.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for cooperatively treating acid mist by wet desulfurization of acid making tail gas comprises the following steps:
(1) Spraying the tail gas to be treated with an ammonium sulfate solution with the mass percent concentration of less than 35%, performing gas-liquid contact collision, and performing countercurrent contact with an aqueous solution containing ammonium sulfate and ammonium sulfite with the pH value of 2-4 to obtain the tail gas at 20-30 ℃;
(2) Then reacts with absorption liquid with pH value of 4-6 to obtain tail gas after tail absorption; the absorption liquid is an aqueous solution containing ammonium sulfate and ammonium sulfite with the mass percentage concentration of 10-25%;
(3) The tail gas after tail absorption is sprayed and washed by an ammonium sulfate aqueous solution with the density of 1.02-1.06 kg/L, then sprayed and washed by an ammonium sulfate aqueous solution with the density of less than 1.02kg/L, and then discharged by a demisting device.
Preferably, the mass ratio of the ammonium sulfate to the ammonium sulfite in the step (1) or the step (2) is 1-5:1.
Particularly preferably, the mass ratio of the ammonium sulfate to the ammonium sulfite in the step (1) or the step (2) is 3:1.
The device for removing the acid mist by using the method comprises a tail absorption tower, a secondary process water tank and a flushing water tank, wherein the secondary process water tank and the flushing water tank are arranged outside the tail absorption tower; the tail gas suction tower is provided with a tail gas inlet and a tail gas outlet; a concentration cooling section, an absorption section, an ammonia demisting section and a combined super demister are sequentially arranged in the tail gas absorption tower according to the flow direction of the tail gas between the tail gas inlet and the tail gas outlet;
the combined super demister sequentially comprises a first-stage demister, a first-stage demister section spray device, a second-stage demister spray device, a third-stage demister and a third-stage demister spray device according to the flow direction of tail gas; the secondary process water tank is connected with the primary demisting section spraying device through a secondary process water pump in a pipeline; the flushing water tank is respectively connected with the two-stage demister spraying device and the three-stage demister spraying device through pipelines by a third water washing pump.
Preferably, the number of the secondary demisters is three, and the number of the secondary demister spraying devices is matched with the number of the secondary demisters; the quantity of tertiary defroster is two sets of, tertiary defroster spray set's quantity with the quantity phase-match of tertiary defroster.
Preferably, the device also comprises a primary process water tank arranged outside the tail absorption tower; the primary process water tank is respectively communicated with the secondary process water tank and the tail absorption tower through pipelines; the secondary process water tank is communicated with an external device for containing flushing fluid through a first process water pipe.
Preferably, the device further comprises a concentration circulation tank which is arranged in the tail gas absorption tower and is positioned below the tail gas inlet;
the concentration cooling section sequentially comprises a concentration cooling section reverse spray sprayer, a concentration cooling section forward spray sprayer and a first aeration disc according to the flow direction of tail gas;
the absorption section sequentially comprises a plurality of absorption section spraying devices and a second air lifting disk according to the flow direction of tail gas;
the ammonia demisting section sequentially comprises an ammonia demister, an ammonia demister section spraying device and a third air lifting disk according to the flow direction of tail gas;
the device also comprises an oxidation circulation tank arranged outside the tail absorption tower; the oxidation circulation tank is divided into an absorption circulation tank and an oxidation tank by a porous partition plate; the absorption circulating groove is respectively communicated with the first air lifting disc and the ammonia water pipeline through pipelines, and is also communicated with the absorption section spraying device through an absorption pump; the oxidation tank is respectively communicated with the absorption section and the concentration circulation tank through pipelines;
the primary process water tank is communicated with the second air lifting disc through a pipeline; the secondary process water tank is communicated with the third air lifting disc through a pipeline;
the device also comprises a primary process water pump; the primary process water pump is respectively communicated with the primary process water tank and the ammonia demister section spraying device through pipelines;
the device also comprises a concentration pump; the concentration pump is respectively communicated with the concentration circulation tank and the concentration cooling section reverse spray sprayer through pipelines;
the device also comprises a delivery pump; the conveying pump is communicated with the concentration circulating tank through a pipeline;
the stirring pump is also included; the stirring pump is respectively communicated with the concentration circulation tank through a pipeline;
the device also comprises a secondary process water pump; and the secondary process water pump is respectively communicated with the secondary process water tank and the primary demisting section spraying device through pipelines.
Preferably, the number of the spraying devices of the absorption section is 3 groups.
Preferably, the flushing water tank is communicated with an external device for containing flushing liquid through a second process water pipe.
By adopting the technical scheme, through the contact collision of solutions with different pH values, the water washing of the ammonium sulfate aqueous solution with high density and low density is combined, after demisting, the detection is carried out through the standard of the ion chromatography for determination of sulfuric acid mist of waste gas with fixed pollution sources (HJ 544-2016), the removal rate of acid mist in the tail gas of the gas outlet exceeds 90 percent relative to the tail gas of the gas inlet, the acid mist removal requirement of the latest standard is completely met, and the acid mist is controlled at 25mg/Nm 3 The following is given. Can also control the sulfur dioxide in the clean tail gas after desulfurization to be 15mg/Nm 3 The following are free NH 3 ≤2mg/Nm 3 . In order to improve the acid mist removal rate and the desulfurization rate from the source and reduce the acid mist, aerosol and free ammonia, an external oxidation circulation tank is independently arranged; the equipment model selection can be more reasonably carried out according to different tail gas conditions, so that the investment is reduced; the tail absorption tower height is reduced, the energy consumption is reduced, and the method is suitable for different SO 2 Concentration and acid mist concentration.
Drawings
Fig. 1 is a schematic structural view of the present invention.
In the figure, a 1-tail gas absorption tower, a 2-tail gas inlet, a 3-concentration circulating tank, a 5-concentration cooling section, a 6-concentration cooling section reverse spray sprayer, a 7-concentration cooling section forward spray sprayer, an 8-first lift disk, a 9-absorption section, a 10-absorption section spray device, an 11-second lift disk, a 12-ammonia demister, a 13-ammonia demister, a 14-ammonia demister section spray device, a 15-third lift disk, a 16-combined super demister, a 17-first stage demister, a 18-first stage demister spray device, a 19-second stage demister, a 20-second stage demister spray device, a 21-third stage demister, a 22-third stage demister spray device, a 23-tail gas outlet, a 24-oxidation circulating tank, a 25-absorption pump, a 26-absorption circulating tank, a 27-perforated baffle, a 28-oxidation tank, a 29-first stage process water pump, a 31-concentration pump, a 32-delivery pump, a 33-stirring pump, a 34-second stage process water tank, a 35-second stage process water pump, a 36-second stage process water pump, a 37-third process water tank, a 39-third process water tank and a water pipe.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
A method for cooperatively treating acid mist by wet desulfurization of acid making tail gas comprises the following steps:
(1) Removing the concentration section; spraying the tail gas to be treated (the temperature is 70-100 ℃) with an ammonium sulfate solution with the mass percent concentration of less than 35%, performing gas-liquid contact collision, and then performing countercurrent contact with an aqueous solution containing ammonium sulfate and ammonium sulfite with the pH value of 3 to obtain the tail gas with the temperature of 20-30 ℃; the mass ratio of the ammonium sulfate to the ammonium sulfite is 3:1.
(2) Removing the absorption section; then reacts with absorption liquid with pH value of 5 to obtain tail gas after tail absorption; the absorption liquid is an aqueous solution containing ammonium sulfate and ammonium sulfite with the mass percentage concentration of 20%; the mass ratio of the ammonium sulfate to the ammonium sulfite is 3:1.
(3) Removing the water washing defogging section; the tail gas after tail absorption is sprayed and washed by an ammonium sulfate aqueous solution with the density of 1.02-1.06 kg/L, then sprayed and washed by an ammonium sulfate aqueous solution with the density of less than 1.02kg/L, and then discharged by a demisting device.
Example 2
A method for cooperatively treating acid mist by wet desulfurization of acid making tail gas comprises the following steps:
(1) Removing the concentration section; spraying the tail gas to be treated (the temperature is 70-100 ℃) with an ammonium sulfate solution with the mass percent concentration of less than 35%, performing gas-liquid contact collision, and then performing countercurrent contact with an aqueous solution containing ammonium sulfate and ammonium sulfite with the pH value of 4 to obtain the tail gas with the temperature of 20-30 ℃; the mass ratio of the ammonium sulfate to the ammonium sulfite is 5:1.
(2) Removing the absorption section; then reacts with absorption liquid with pH value of 6 to obtain tail gas after tail absorption; the absorption liquid is an aqueous solution containing ammonium sulfate and ammonium sulfite with the mass percentage concentration of 25%; the mass ratio of the ammonium sulfate to the ammonium sulfite is 5:1.
(3) Removing the water washing defogging section; the tail gas after tail absorption is sprayed and washed by an ammonium sulfate aqueous solution with the density of 1.02-1.06 kg/L, then sprayed and washed by an ammonium sulfate aqueous solution with the density of less than 1.02kg/L, and then discharged by a demisting device.
Example 3
A method for cooperatively treating acid mist by wet desulfurization of acid making tail gas comprises the following steps:
(1) Removing the concentration section; spraying the tail gas to be treated (the temperature is 70-100 ℃) with an ammonium sulfate solution with the mass percent concentration of less than 35%, performing gas-liquid contact collision, and then performing countercurrent contact with an aqueous solution containing ammonium sulfate and ammonium sulfite with the pH value of 2 to obtain the tail gas with the temperature of 20-30 ℃; the mass ratio of the ammonium sulfate to the ammonium sulfite is 1:1.
(2) Removing the absorption section; then reacts with absorption liquid with pH value of 4 to obtain tail gas after tail absorption; the absorption liquid is an aqueous solution with the mass percent concentration of 10% and containing ammonium sulfate and ammonium sulfite; the mass ratio of the ammonium sulfate to the ammonium sulfite is 1:1.
(3) Removing the water washing defogging section; the tail gas after tail absorption is sprayed and washed by an ammonium sulfate aqueous solution with the density of 1.02-1.06 kg/L, then sprayed and washed by an ammonium sulfate aqueous solution with the density of less than 1.02kg/L, and then discharged by a demisting device.
The above embodiment is detected by the standard of ion chromatography for measuring sulfuric acid mist of exhaust gas with fixed pollution source (HJ 544-2016), and the removal rate of acid mist in the exhaust gas at the gas outlet exceeds 90% relative to the exhaust gas at the gas inlet, thereby completely meeting the acid mist removal requirement of the latest standard, and controlling the acid mist to be 25mg/Nm 3 The following is given.
Wherein, the acid mist removal efficiency of the concentration section is 30-35%, the acid mist removal efficiency of the absorption section is 40-45%, and the acid mist removal efficiency of the water washing defogging section is 75-80%.
In order to embody the technical effects of the invention, the following tests are specially made for comparison.
Comparative example 1
On the basis of the embodiment 1, in the stage of removing in the concentration section, other conditions are unchanged, and the ammonium sulfate solution with the mass percent concentration of more than 35% is selected to contact and collide with the tail gas with relatively high temperature (70-100 ℃) to be treated, and particularly, the ammonium sulfate solution with the mass percent concentration of 36%, 37%, 38%, 39% and 40% is selected.
Experiments show that as the concentration increases, the crystallization of the ammonium sulfate solution can be caused, so that the acid mist removal efficiency of the concentration section is low and is about within 15%, and the efficiency of the concentration section is not in a linear relation with the concentration. Compared with the acid mist removal efficiency within 35%, the acid mist removal efficiency is obviously reduced, and the final tail gas does not meet the latest standard.
Comparative example 2
On the basis of example 1, in the stage of removal in the concentration section, other conditions are unchanged, and the aqueous solution containing ammonium sulfate and ammonium sulfite with pH value less than 2 or more than 4 is selected to contact the tail gas in countercurrent. Specifically, a pH of 1.5, 1, 4.5 or 5 is selected.
Experiments show that when the pH value is less than 2, equipment is easy to corrode due to strong acidity, the acid mist removal efficiency of the concentration section is within 25%, and the final tail gas does not meet the latest standard. When the pH value is more than 4, the acid mist removal efficiency of the concentration section is within 20%, and the final tail gas does not meet the latest standard. It can be seen that the acid mist removal efficiency does not show a linear relationship with the increase of the pH value, and the change of the pH value has obvious influence on the acid mist removal.
Comparative example 3
Based on example 1, in the stage of removal in the concentration section, other conditions are unchanged, and different mass ratios of ammonium sulfate to ammonium sulfite are selected when the aqueous solution containing ammonium sulfate and ammonium sulfite contacts the tail gas in countercurrent. When the mass ratio of the ammonium sulfate to the ammonium sulfite is greater than 5:1 or when the mass ratio of the ammonium sulfate to the ammonium sulfite is less than 1:1. Specifically, the mass ratio of the ammonium sulfate to the ammonium sulfite is 6:1 or 7:1, the concentration of the ammonium sulfate is too large, crystallization is easy to occur, acid mist absorption is not facilitated, and the acid mist removal efficiency is low and is about within 25%; when the mass ratio of ammonium sulfate to ammonium sulfite is 1:2 or 1:3, the concentration of ammonium sulfite is too high, so that the oxidation efficiency is reduced, and the generation of new acid mist is also caused while acid mist is removed, so that the concentration of ammonium sulfite cannot be too high. Therefore, the quality ratio of the ammonium sulfate to the ammonium sulfite can obviously influence the removal efficiency of acid mist and influence whether the final tail gas meets the requirements of new standards.
Comparative example 4
On the basis of example 1, in the stage of removing the absorption section, other conditions are unchanged, and the absorption liquid with the pH value less than 4 or more than 6 is selected for reaction. Specifically, a pH of 3, 3.5, 6.5 or 7 is selected.
Experiments show that when the pH value is less than 4, the acid mist removal efficiency is within 31%, and the final tail gas does not meet the latest standard. When the pH value is more than 6, the acid mist removal efficiency is within 24%, and the final tail gas does not meet the latest standard. Therefore, the acid mist removal efficiency does not show a linear relationship with the increase of the pH value, and the change of the pH value of the absorption liquid has obvious influence on the acid mist removal.
Comparative example 5
On the basis of example 1, in the stage of removing the absorption section, other conditions are unchanged, and an aqueous solution containing ammonium sulfate and ammonium sulfite with the mass percent concentration of the absorption liquid being less than 10% or an aqueous solution containing ammonium sulfate and ammonium sulfite with the mass percent concentration of the absorption liquid being more than 25% is selected for research. Specifically, 35%, 30%, 28%, 8%, 5% or 1% is selected.
Experiments show that when the mass percentage concentration of the absorption liquid is more than 25%, ammonia can escape, and new acid mist can be generated after the acid mist is removed, so that the selection is not suitable. When the mass percentage concentration of the absorption liquid is less than 10%, the acid mist removal efficiency is within 30%, and the final tail gas does not meet the latest standard.
Comparative example 6
Based on the example 1, in the stage of removing the absorption section, other conditions are unchanged, and different mass ratios of ammonium sulfate to ammonium sulfite are selected in the absorption liquid. When the mass ratio of the ammonium sulfate to the ammonium sulfite is greater than 5:1 or when the mass ratio of the ammonium sulfate to the ammonium sulfite is less than 1:1. Specifically, the mass ratio of the ammonium sulfate to the ammonium sulfite is 6:1 or 7:1, the concentration of the ammonium sulfate is too high, crystallization is easy to occur, acid mist absorption is not facilitated, and the acid mist removal efficiency is low and is about within 28%; when the mass ratio of ammonium sulfate to ammonium sulfite is 1:2 or 1:3, the concentration of ammonium sulfite is too high, so that the oxidation efficiency is reduced, and the generation of new acid mist is also caused while acid mist is removed, so that the concentration of ammonium sulfite cannot be too high. Therefore, the quality ratio of the ammonium sulfate to the ammonium sulfite can obviously influence the removal efficiency of acid mist and influence whether the final tail gas meets the requirements of new standards.
Comparative example 7
On the basis of the embodiment 1, in the stage of removing the water washing demisting section, other conditions are unchanged, the water washing is firstly performed by spraying the ammonium sulfate aqueous solution with the density of less than 1.02kg/L or more than 1.06kg/L, and then the water washing is performed by spraying the ammonium sulfate aqueous solution with the density of less than 1.02 kg/L.
Experiments show that the ammonium sulfate aqueous solution with the concentration of more than 1.06kg/L is sprayed and washed, is easy to crystallize, is unfavorable for removing acid mist, and has low acid mist removing efficiency within about 32 percent; the ammonium sulfate aqueous solution with the concentration of less than 1.02kg/L is sprayed and washed, so that the acid mist removal is not facilitated, and the acid mist removal efficiency is low within about 40%.
Comparative example 8
On the basis of the embodiment 1, in the stage of removing the water washing demisting section, other conditions are unchanged, firstly, the water washing is performed by spraying the ammonium sulfate aqueous solution with the density of 1.02-1.06 kg/L, and then the water washing is performed by spraying the ammonium sulfate aqueous solution with the density of more than 1.02 kg/L.
Experiments show that the ammonium sulfate aqueous solution with the concentration of more than 1.02kg/L is sprayed and washed, so that the acid mist removal is unfavorable, the acid mist removal efficiency is low and is about within 45%, and the final tail gas does not meet the requirements of new standards.
In summary, it can be seen that the efficiency of acid mist removal is affected by different process changes or technical parameter changes, so that the tail gas treatment does not meet the requirements of new standards. Therefore, the acid mist can be effectively removed only by the mutual cooperation of the working procedures.
In order to match with higher acid mist removal efficiency, the process provided by the invention is combined, and a device for removing acid mist is also researched. As shown in fig. 1, an apparatus for removing acid mist by the method of any one of examples 1 to 3 comprises a tail absorption tower 1, and further comprises a secondary process water tank 34 and a flushing water tank 36 which are arranged outside the tail absorption tower 1; the tail gas suction tower 1 is provided with a tail gas inlet 2 and a tail gas outlet 23; a concentration cooling section 5, an absorption section 9, an ammonia demisting section 12 and a combined super demister 16 are sequentially arranged in the tail gas absorption tower 1 in the tail gas flowing direction between the tail gas inlet 2 and the tail gas outlet 23;
the combined super demister 16 sequentially comprises a first-stage demister 17, a first-stage demister section spray device 18, a second-stage demister 19, a second-stage demister spray device 20, a third-stage demister 21 and a third-stage demister spray device 22 according to the flow direction of tail gas; the secondary process water tank 34 is connected with the primary demisting section spraying device 18 through a secondary process water pump 35 in a pipeline; the flushing tank 36 is in pipe connection with the secondary mist eliminator spraying device 20 and the tertiary mist eliminator spraying device 22, respectively, by a third water washing pump 37.
Specifically, in order to improve the demisting effect, the number of the secondary demisters 19 is three, and the number of the secondary demister spraying devices 20 is matched with the number of the secondary demisters 19; the number of the three-stage demisters 21 is two, and the number of the three-stage demister spraying devices 22 is matched with the number of the three-stage demisters 21.
Also comprises a primary process water tank 29 arranged outside the tail absorption tower 1; the primary process water tank 29 is respectively communicated with the secondary process water tank 34 and the tail absorption tower 1 through pipelines; the secondary process water tank 34 communicates with an external device for holding rinse liquid via a first process water line 38.
The device also comprises a concentration circulation tank 3 which is arranged in the tail gas absorption tower 1 and is positioned below the tail gas inlet 2; the concentration cooling section 5 sequentially comprises a concentration cooling section reverse spray sprayer 6, a concentration cooling section forward spray sprayer 7 and a first lift disc 8 according to the flow direction of tail gas; the absorption section 9 sequentially comprises a plurality of absorption section spraying devices 10 and a second air lifting disc 11 according to the flow direction of tail gas; the ammonia demister section 12 sequentially comprises an ammonia demister 1), an ammonia demister section spraying device 14 and a third lift disc 15 according to the flow direction of tail gas;
also comprises an oxidation circulation tank 24 arranged outside the tail absorption tower 1; the oxidation circulation tank 24 is divided into an absorption circulation tank 26 and an oxidation tank 28 by a perforated partition plate 27; the absorption circulation groove 26 is respectively communicated with the first lift disc 8 and the ammonia water pipeline 40 through pipelines, and is also communicated with the absorption section spraying device 10 through an absorption pump 25; the oxidation tank 28 is respectively communicated with the absorption section 9 and the concentration circulation tank 3 through pipelines; the primary process water tank 29 is communicated with the second lift disc 11 through a pipeline; the secondary process water tank 34 is communicated with the third lift disc 15 through a pipeline;
also included is a primary process water pump 30; the primary process water pump 30 is respectively communicated with the primary process water tank 29 and the ammonia demister section spraying device 14 through pipelines;
further comprising a concentrate pump 31; the concentration pump 31 is respectively communicated with the concentration circulation tank 3 and the concentration cooling section reverse spray sprayer 6 through pipelines;
also included is a transfer pump 32; the delivery pump 32 is communicated with the concentration circulation tank 3 through a pipeline;
further comprising a stirring pump 33; the stirring pumps 33 are respectively communicated with the concentration circulation tank 3 through pipelines;
also comprises a secondary process water pump 35; the secondary process water pump 35 is respectively communicated with the secondary process water tank 34 and the primary demisting section spraying device 18 through pipelines.
Specifically, the number of absorption stage spray devices 10 is 3. The rinse water tank 36 communicates with an external device for holding rinse water through a second process water pipe 39.
Through the combined action of the process and the device, the acid mist has high stripping rate (more than or equal to 90 percent), high desulfurization efficiency (more than or equal to 99 percent), the discharged tail gas SO2 is less than or equal to 15mg/Nm3, the acid mist is less than or equal to 25mg/Nm3, the free NH3 is less than or equal to 2mg/Nm3, the byproduct is almost undetectable by the inferior salt when the ammonium sulfate solution is sent out, and the quality of the byproduct ammonium sulfate can reach the grade of ammonium sulfate (GB 535) after the byproduct ammonium sulfate is dried. The equipment can be selected according to different tail gas conditions, so that the investment is reduced.
The embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.

Claims (4)

1. The method for cooperatively treating the acid mist by wet desulfurization of the tail gas of acid production is characterized by adopting a device for removing the acid mist, wherein the device comprises a tail absorption tower (1), and further comprises a secondary process water tank (34) and a flushing water tank (36) which are arranged outside the tail absorption tower (1); a tail gas inlet (2) and a tail gas outlet (23) are formed in the tail gas absorbing tower (1); a concentration cooling section (5), an absorption section (9), an ammonia demisting section (12) and a combined super demister (16) are sequentially arranged in the tail gas absorption tower (1) between the tail gas inlet (2) and the tail gas outlet (23) according to the flow direction of the tail gas;
the combined super demister (16) sequentially comprises a first-stage demister (17), a first-stage demister section spray device (18), a second-stage demister (19), a second-stage demister spray device (20), a third-stage demister (21) and a third-stage demister spray device (22) according to the flow direction of tail gas; the secondary process water tank (34) is connected with the primary demisting section spraying device (18) through a secondary process water pump (35); the flushing water tank (36) is respectively connected with the two-stage demister spraying device (20) and the three-stage demister spraying device (22) through a third water washing pump (37) in a pipeline manner;
the device also comprises a concentration circulation tank (3) which is arranged in the tail gas absorption tower (1) and is positioned below the tail gas inlet (2);
the concentration cooling section (5) sequentially comprises a concentration cooling section reverse spray sprayer (6), a concentration cooling section forward spray sprayer (7) and a first aeration disc (8) according to the flow direction of tail gas;
the absorption section (9) sequentially comprises a plurality of absorption section spraying devices (10) and a second air lifting disc (11) according to the flow direction of tail gas;
the ammonia demisting section (12) sequentially comprises an ammonia demister (13), an ammonia demister section spraying device (14) and a third air lifting disc (15) according to the flow direction of tail gas;
the device also comprises an oxidation circulation tank (24) arranged outside the tail absorption tower (1); the oxidation circulation tank (24) is divided into an absorption circulation tank (26) and an oxidation tank (28) by a perforated partition plate (27); the absorption circulation groove (26) is respectively communicated with the first air lifting disc (8) and the ammonia water pipeline (40) through pipelines, and is also communicated with the absorption section spraying device (10) through an absorption pump (25); the oxidation tank (28) is respectively communicated with the absorption section (9) and the concentration circulation tank (3) through pipelines;
the primary process water tank (29) is communicated with the second air lifting disc (11) through a pipeline; the secondary process water tank (34) is communicated with the third air lifting disc (15) through a pipeline;
the device also comprises a primary process water pump (30); the primary process water pump (30) is respectively communicated with the primary process water tank (29) and the ammonia demister section spraying device (14) through pipelines;
further comprises a concentration pump (31); the concentration pump (31) is respectively communicated with the concentration circulation tank (3) and the concentration cooling section reverse spray sprayer (6) through pipelines;
further comprises a delivery pump (32); the conveying pump (32) is communicated with the concentration circulation tank (3) through a pipeline;
further comprising a stirring pump (33); the stirring pump (33) is respectively communicated with the concentration circulation tank (3) through a pipeline;
the device also comprises a secondary process water pump (35); the secondary process water pump (35) is respectively communicated with the secondary process water tank (34) and the primary demisting section spraying device (18) through pipelines;
the number of the absorbing section spraying devices (10) is 3 groups;
the flushing water tank (36) is communicated with an external device for containing flushing liquid through a second process water pipe (39);
the method comprises the following steps:
(1) Spraying the tail gas to be treated with an ammonium sulfate solution with the mass percent concentration of less than 35%, performing gas-liquid contact collision, and performing countercurrent contact with an aqueous solution containing ammonium sulfate and ammonium sulfite with the pH value of 2-4 to obtain the tail gas at 20-30 ℃;
(2) Then reacts with absorption liquid with pH value of 4-6 to obtain tail gas after tail absorption; the absorption liquid is an aqueous solution containing ammonium sulfate and ammonium sulfite with the mass percentage concentration of 10-25%;
(3) The tail gas after tail absorption is sprayed and washed by an ammonium sulfate aqueous solution with the density of 1.02-1.06 kg/L, then sprayed and washed by an ammonium sulfate aqueous solution with the density of less than 1.02kg/L, and then discharged by a demisting device.
2. The method for the synergistic treatment of acid mist by wet desulfurization of acid making tail gas according to claim 1, wherein the mass ratio of ammonium sulfate to ammonium sulfite in the step (1) or the step (2) is 1-5:1.
3. The method for cooperatively treating acid mist by wet desulfurization of acid making tail gas according to claim 1, which is characterized in that: the number of the secondary demisters (19) is three, and the number of the secondary demister spraying devices (20) is matched with the number of the secondary demisters (19); the number of the three-stage demisters (21) is two, and the number of the three-stage demister spraying devices (22) is matched with the number of the three-stage demisters (21).
4. The method for cooperatively treating acid mist by wet desulfurization of acid making tail gas according to claim 1, which is characterized in that: the device also comprises a primary process water tank (29) arranged outside the tail absorption tower (1); the primary process water tank (29) is respectively communicated with the secondary process water tank (34) and the tail absorption tower (1) through pipelines; the secondary process water tank (34) is communicated with an external device for containing flushing liquid through a first process water pipe (38).
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