CN211886185U - Device of minimum emission of gypsum system sulphuric acid byproduct cement device tail gas - Google Patents

Device of minimum emission of gypsum system sulphuric acid byproduct cement device tail gas Download PDF

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CN211886185U
CN211886185U CN202020250875.8U CN202020250875U CN211886185U CN 211886185 U CN211886185 U CN 211886185U CN 202020250875 U CN202020250875 U CN 202020250875U CN 211886185 U CN211886185 U CN 211886185U
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gas
tower
sulfuric acid
desulfurizing tower
tail gas
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吕天宝
高强
冯祥义
鲍树涛
王同永
袁金亮
王树才
武健民
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Shandong Lubei Enterprise Group Co
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Shandong Lubei Enterprise Group Co
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/10Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

The utility model relates to the technical field of industrial waste gas comprehensive treatment, in particular to a device for ultralow emission of tail gas of a device for producing sulfuric acid and byproduct cement from gypsum, which comprises a gas-gas reactor, a sulfuric acid secondary absorption tower, a primary desulfurization tower, a secondary desulfurization tower and a demister, wherein the gas-gas reactor, the sulfuric acid secondary absorption tower, the primary desulfurization tower, the secondary desulfurization tower and the demister are sequentially connected by pipelines; the gas-gas reactor is provided with an ozone generator; the sulfuric acid secondary absorption tower is provided with a sulfuric acid inlet and a sulfuric acid outlet, and the sulfuric acid outlet is communicated with a sulfuric acid product storage tank pipeline through a pipeline. The device not only can realize denitrogenation, desulfurization effect, can also guarantee effectively getting rid of particulate matter and sulfuric acid mist.

Description

Device of minimum emission of gypsum system sulphuric acid byproduct cement device tail gas
Technical Field
The utility model relates to an industrial waste gas comprehensive treatment technical field, concretely relates to device that gypsum system sulphuric acid byproduct cement device tail gas minimum was discharged.
Background
According to the related laws and regulations of the environmental protection act of the people's republic of China and the air pollution prevention and treatment act of the people's republic of China, particularly the notice of the Notification about the urban execution of the special emission limit of the air pollutants in the air pollution transmission channel of Jingjin Ji issued by the environmental protection department of 2018, 1, 15 days (No. 9 of 2018), the cement plant is required to execute the flue gas SO2The content is less than 100mg/m3Nitrogen oxidation ofThe content of the substance is less than 320mg/m3The content of the particles is less than 20mg/m3(ii) a Flue gas SO of sulfuric acid plant2The content is less than 200mg/m3Sulfuric acid mist (SO)3) The content is less than 5mg/m3. Governments around the world are setting and developing more stringent local standards.
The most widely used desulfurization, denitrification and dust removal technologies at present mainly comprise wet flue gas desulfurization and reduction denitration, oxidation absorption denitration and wet dust removal combined technologies, wherein the wet desulfurization process generally needs to be operated below 150 ℃ to achieve ideal desulfurization efficiency; the selective non-catalytic reduction (SNCR) temperature range is 870-1000 ℃, the denitration rate is about 50%, the flue gas temperature is controlled to be 250-420 ℃ in Selective Catalytic Reduction (SCR), and the denitration rate can reach 75-90%.
CaSO decomposition device for preparing sulfuric acid and byproduct cement from gypsum4Generate SO at the same time2Nitrogen Oxide (NO)x) Sulfuric acid mist (SO)3) And particulate matters and the like, the temperature of the exhaust gas and the tail gas discharged in the acid production from gypsum is lower, the discharge temperature is about 75 ℃, and the traditional SCR and SNCR processes can not be applied, so that a new device capable of improving the desulfurization and denitration efficiency and the dust and sulfuric acid mist removal effect is inevitably researched and developed to meet the increasingly strict requirements of environmental protection policies.
SUMMERY OF THE UTILITY MODEL
Lack the technical problem who is applicable to the processing apparatus of the tail gas that gypsum system sulfuric acid by-product cement produced to prior art, the utility model provides a device of the ultralow emission of gypsum system sulfuric acid by-product cement device tail gas. The device not only can realize denitrogenation, desulfurization effect, can also guarantee effectively getting rid of particulate matter and sulfuric acid mist.
A device for ultralow emission of tail gas of a device for preparing sulfuric acid and byproduct cement from gypsum comprises a gas-gas reactor, a sulfuric acid secondary absorption tower, a primary desulfurization tower, a secondary desulfurization tower and a demister, which are sequentially connected by pipelines;
the gas-gas reactor is provided with an ozone generator;
the sulfuric acid secondary absorption tower is provided with a sulfuric acid inlet and a sulfuric acid outlet, and the sulfuric acid outlet is communicated with a sulfuric acid product storage tank pipeline through a pipeline.
Further, the gas-gas reactor is a micro gasification gas-gas reactor. The reactor has the advantages of small volume, low pressure drop, short reaction time, high speed, stable operation, no vibration, continuous process, easy control and the like, and is a production micro reactor which can realize process enhancement, safety and high efficiency.
Further, the gas-gas reactor is arranged in a working condition section with the pipeline temperature less than or equal to 150 ℃ in front of the sulfuric acid secondary absorption tower. Too low a temperature affects the denitration effect, and too high a temperature increases the decomposition loss rate of ozone.
Furthermore, an annular gas distribution device, a tail gas air pipe and a tail gas reactor are also arranged on the gas-gas reactor. Ozone gas from the ozone generator is uniformly introduced into the section of a tail gas air pipe to be treated through an annular gas distribution device, and then the tail gas is enabled to generate turbulent flow through a tail gas reactor, so that ozone and NO in the tail gas are ensuredxCan be sufficiently contacted to react.
Furthermore, the total pressure loss of the annular gas distribution device and the tail gas reactor is not more than 300 Pa.
Further, the one-level desulfurizing tower includes the one-level desulfurizing tower body and sets up the ammonia tank in the one-level desulfurizing tower body outside, supreme one-level desulfurizing tower reservoir, the import of one-level desulfurizing tower tail gas, the one-level desulfurizing tower that include in proper order spray layer and one-level desulfurizing tower tail gas export are down followed to the inside of one-level desulfurizing tower body, one-level desulfurizing tower reservoir and one-level desulfurizing tower spray and still are equipped with one-level desulfurizing tower air intlet between the layer, the one-level desulfurizing tower sprays the layer and is connected with the ammonia tank through the pipeline, the one-level desulfurizing tower reservoir passes through the pipeline and is connected.
Further, the second grade desulfurizing tower includes the second grade desulfurizing tower body and sets up the limestone absorption agent thick liquid case in the second grade desulfurizing tower body outside, inside from the bottom up of second grade desulfurizing tower body includes second grade desulfurizing tower reservoir, second grade desulfurizing tower tail gas import, second grade desulfurizing tower in proper order and sprays layer and second grade desulfurizing tower tail gas export, second grade desulfurizing tower reservoir and second grade desulfurizing tower spray and still are equipped with second grade desulfurizing tower air intlet between the layer, the second grade desulfurizing tower sprays the layer and passes through the pipeline and be connected with limestone absorption agent thick liquid case, the second grade desulfurizing tower reservoir passes through the pipeline and is connected with gypsum system sulphuric acid by-product cement device.
Further, the demister is a two-stage wet-type electric demister connected in series.
The utility model discloses a theory of operation:
the tail gas of the device for preparing sulfuric acid and byproduct cement from gypsum has nitrogen oxide which is a kiln component and has higher content of sulfur dioxide and sulfuric acid mist (SO) in a sulfuric acid device3) Firstly, tail gas enters a gas-gas reactor, an ozone generator generates ozone, the ozone is mixed with NOx in the tail gas to react, and nitric oxide in the tail gas is oxidized into high-price nitric oxide;
then the tail gas passes through a sulfuric acid secondary absorption tower, and NO which is easily dissolved in water in the tail gasxThe sulfuric acid can be used as a product to be stored in a sulfuric acid product storage tank;
then the tail gas is subjected to two-stage desulfurization by an ammonia method and a calcium method in sequence in a first-stage desulfurization tower and a second-stage desulfurization tower, ammonium sulfate enters a diammonium phosphate production device, desulfurized gypsum enters a gypsum sulfuric acid byproduct cement preparation device again, and simultaneously ozone which is not completely consumed in the tail gas is decomposed in the desulfurization process;
and finally, removing particles and sulfuric acid mist from the tail gas through a demister.
The device for ultralow emission of tail gas of the device for preparing sulfuric acid by-product cement from gypsum has the advantages that,
the structure is reasonable in design, the operation cost is low, all emission indexes are qualified, and the ultra-low emission indexes are achieved;
secondly, the first desulfurizing tower is desulfurized by an ammonia method, and ammonia escape can be avoided in the desulfurizing process by controlling the pH value of the desulfurizing tower to be 2-4;
③ NO formed in the tail gas treatment processxThe diammonium phosphate and the desulfurized gypsum realize resource utilization, and are economical and environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of embodiment 1 of the present invention;
fig. 2 is a schematic structural diagram of embodiment 2 of the present invention;
FIG. 3 is a schematic structural view of a primary desulfurization tower of the present invention;
fig. 4 is a schematic structural diagram of the second-stage desulfurizing tower of the present invention.
In the figure, a 1-gas reactor, a 2-sulfuric acid secondary absorption tower, a 3-primary desulfurization tower, a 4-secondary desulfurization tower, a 5-demister, a 6-sulfuric acid product storage tank, a 7-diammonium phosphate production device and an 8-gypsum sulfuric acid byproduct cement preparation device are arranged;
31-a first-stage desulfurizing tower body, 32-an ammonia water tank, 33-a first-stage desulfurizing tower liquid storage tank, 34-a first-stage desulfurizing tower tail gas inlet, 35-a first-stage desulfurizing tower spraying layer, 36-a first-stage desulfurizing tower tail gas outlet and 37-a first-stage desulfurizing tower air inlet;
41-a second-stage desulfurizing tower body, 42-a limestone absorbent slurry tank, 43-a second-stage desulfurizing tower liquid storage tank, 44-a second-stage desulfurizing tower tail gas inlet, 45-a second-stage desulfurizing tower spraying layer, 46-a second-stage desulfurizing tower tail gas outlet and 47-a second-stage desulfurizing tower air inlet.
Detailed Description
In order to make the technical solutions in the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative efforts shall belong to the protection scope of the present invention.
Example 1
As shown in fig. 1, a device for ultralow emission of tail gas of a device for producing sulfuric acid and byproduct cement from gypsum, which comprises a gas-gas reactor 1, a sulfuric acid secondary absorption tower 2, a primary desulfurization tower 3, a secondary desulfurization tower 4 and a demister 5 which are sequentially connected by pipelines;
the gas-gas reactor 1 is provided with an ozone generator;
the sulfuric acid secondary absorption tower 2 is provided with a sulfuric acid inlet and a sulfuric acid outlet, and the sulfuric acid outlet is communicated with a sulfuric acid product storage tank 6 through a pipeline;
the pipelines are provided with valves and delivery pumps.
Example 2
As shown in fig. 2, on the basis of example 1,
the gas-gas reactor 1 is a micro gasification gas-gas reactor, the gas-gas reactor 1 is arranged at a working condition section with the temperature of a pipeline in front of the sulfuric acid secondary absorption tower 2 being less than or equal to 150 ℃, the gas-gas reactor 1 is also provided with an annular gas distribution device, a tail gas air pipe and a tail gas reactor, the total pressure loss of the annular gas distribution device and the tail gas reactor is not more than 300Pa, and the connection relation of the annular gas distribution device, the tail gas air pipe and the tail gas reactor in the gas-gas reactor 1 is the same as that of the prior art;
the first-stage desulfurizing tower 3 comprises a first-stage desulfurizing tower body 31 and an ammonia water tank 32 arranged on the outer side of the first-stage desulfurizing tower body 31, the first-stage desulfurizing tower liquid storage tank 33 is sequentially arranged in the first-stage desulfurizing tower body 31 from bottom to top, the first-stage desulfurizing tower tail gas inlet 34, the first-stage desulfurizing tower spraying layer 35 and the first-stage desulfurizing tower tail gas outlet 36 are arranged, a first-stage desulfurizing tower air inlet 37 is also arranged between the first-stage desulfurizing tower liquid storage tank 33 and the first-stage desulfurizing tower spraying layer 35, the first-stage desulfurizing tower spraying layer 35 is connected with the ammonia water tank 32 through a pipeline, and the first-stage desulfurizing tower liquid storage tank 33;
the second-stage desulfurizing tower 4 comprises a second-stage desulfurizing tower body 41 and a limestone absorbent slurry tank 42 arranged outside the second-stage desulfurizing tower body 41, the second-stage desulfurizing tower liquid storage tank 43, a second-stage desulfurizing tower tail gas inlet 44, a second-stage desulfurizing tower spraying layer 45 and a second-stage desulfurizing tower tail gas outlet 46 are sequentially arranged in the second-stage desulfurizing tower body 41 from bottom to top, a second-stage desulfurizing tower air inlet 47 is further arranged between the second-stage desulfurizing tower liquid storage tank 43 and the second-stage desulfurizing tower spraying layer 45, the second-stage desulfurizing tower spraying layer 45 is connected with the limestone absorbent slurry tank 42 through a pipeline, and the second-stage desulfurizing tower liquid storage tank 43 is connected with a gypsum sulfuric acid byproduct cement device 8 through a pipeline;
the demister 5 is a two-stage wet electric demister connected in series;
the pipelines are provided with valves and delivery pumps.
Example 3
The alkylated waste sulfuric acid is sprayed and burned on a device for producing 10 million tons of sulfuric acid by using gypsum and by-producing 15 million tons of cement in the year, a decomposition and calcination device of the device adopts a phi 4 multiplied by 75m rotary kiln (single kiln operation) with a preheater, and a four-stage cyclone preheater is arranged, and the sulfuric acid is an acid cleaning purification, two-rotation two-absorption and tail gas treatment process.
About 78000Nm3The tail gas enters a gas-gas reactor 1 in front of a sulfuric acid secondary absorption tower 2 at the reaction temperature of 125 +/-3 ℃, and the ozone adding proportion O is controlled3/NOxThe molar ratio is 1:1.25, and about 88 percent of nitric oxide is changed into expensive nitric oxide;
in the sulfuric acid secondary absorption tower 2, NOx which is easily dissolved in water in tail gas is absorbed by concentrated sulfuric acid and water to be changed into nitroso sulfuric acid and nitric acid to enter a sulfuric acid product, and the content of the nitrate in the sulfuric acid product is within 1.2 per thousand by sampling detection and analysis;
the reaction temperature of the first-stage desulfurizing tower 3 is 40-70 ℃, the pH value is controlled to be 3.0, no ammonia escapes, the reaction temperature of the second-stage desulfurizing tower 4 is 27-40 ℃, and the pH value is controlled to be 5.5;
finally, the tail gas enters a two-stage wet type electric demister 5 to remove particulate matters and sulfuric acid mist, and online data of an air outlet shows SO2: 7.5mg/Nm3,NOx:42mg/Nm3And (3) particulate matters: 3.5mg/m3Temperature: and (3) sampling, detecting and analyzing sulfuric acid mist at 28 ℃: 1.66mg/m3
Example 4
The method comprises the steps of (1) carrying out spray firing on a large-scale device for preparing sulfuric acid and co-producing 30 ten thousand of cement by using 20 ten thousand of gypsum produced annually, wherein a decomposition and calcination device adopts a phi 4 x 75m rotary kiln (double-kiln operation) with a preheater, and is provided with a four-stage cyclone preheater, and sulfuric acid is an acid cleaning purification, two-rotation two-absorption and tail gas treatment process;
about 125000Nm3The tail gas enters a gas-gas reactor 1 in front of a sulfuric acid secondary absorption tower 2 at the reaction temperature of 135 +/-3 ℃, and the ozone adding proportion O is controlled3/NOxThe molar ratio is 1:1.35, so that about 90 percent of nitric oxide is changed into expensive nitric oxide;
in the sulfuric acid secondary absorption tower 2, NOx which is easily dissolved in water in tail gas is absorbed by concentrated sulfuric acid and water to be changed into nitroso sulfuric acid and nitric acid to enter a sulfuric acid product, and the content of the nitrate in the sulfuric acid product is within 1.5 per thousand by sampling detection and analysis;
the temperature of the tail gas is reduced after the tail gas passes through the first-level ammonia desulfurization tower and is washed, and the temperature of the tail gas is further reduced after the tail gas passes through the second-level calcium desulfurization tower and is washed; the reaction temperature of the first-stage desulfurizing tower 3 is 50-75 ℃, the pH value is controlled to be 3.2, no ammonia escapes, the reaction temperature of the second-stage desulfurizing tower 4 is 28-50 ℃, and the pH value is controlled to be 5.5;
finally, the tail gas enters a two-stage wet type electric demister 5 to remove particulate matters and sulfuric acid mist, and online data of an air outlet shows SO2: 8.5mg/Nm3,NOx:45mg/Nm3And (3) particulate matters: 3.7mg/m3Temperature: sampling, detecting and analyzing the sulfuric acid mist at 30 ℃ to be 1.84mg/m3
Although the present invention has been described in detail by referring to the drawings in conjunction with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and substance of the present invention, and these modifications or substitutions are intended to be within the scope of the present invention/any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. The device is characterized by comprising a gas-gas reactor (1), a sulfuric acid secondary absorption tower (2), a primary desulfurization tower (3), a secondary desulfurization tower (4) and a demister (5) which are sequentially connected through pipelines;
the gas-gas reactor (1) is provided with an ozone generator;
the sulfuric acid secondary absorption tower (2) is provided with a sulfuric acid inlet and a sulfuric acid outlet, and the sulfuric acid outlet is communicated with a sulfuric acid product storage tank (6) through a pipeline.
2. The apparatus according to claim 1, wherein the gas-gas reactor (1) is a micro gasification gas-gas reactor.
3. The device according to claim 1, characterized in that the gas-gas reactor (1) is arranged in the front pipeline temperature of the sulfuric acid secondary absorption tower (2) at the working condition section of less than or equal to 150 ℃.
4. The apparatus according to claim 1, wherein the gas-gas reactor (1) is further provided with an annular gas distribution device, a tail gas air pipe and a tail gas reactor.
5. The apparatus of claim 4, wherein the total pressure loss of the annular gas distribution device and the tail gas reactor is not more than 300 Pa.
6. The device according to claim 1, wherein the first-stage desulfurizing tower (3) comprises a first-stage desulfurizing tower body (31) and an ammonia tank (32) arranged outside the first-stage desulfurizing tower body (31), the first-stage desulfurizing tower body (31) comprises a first-stage desulfurizing tower liquid storage tank (33), a first-stage desulfurizing tower tail gas inlet (34), a first-stage desulfurizing tower spraying layer (35) and a first-stage desulfurizing tower tail gas outlet (36) from bottom to top in sequence, a first-stage desulfurizing tower air inlet (37) is further arranged between the first-stage desulfurizing tower liquid storage tank (33) and the first-stage desulfurizing tower spraying layer (35), the first-stage desulfurizing tower spraying layer (35) is connected with the ammonia tank (32) through a pipeline, and the first-stage desulfurizing tower liquid storage tank (33) is connected with the diammonium phosphate production device (7) through a pipeline.
7. The device according to claim 1, wherein the secondary desulfurization tower (4) comprises a secondary desulfurization tower body (41) and a limestone absorbent slurry tank (42) arranged outside the secondary desulfurization tower body (41), the secondary desulfurization tower body (41) sequentially comprises a secondary desulfurization tower liquid storage tank (43), a secondary desulfurization tower tail gas inlet (44), a secondary desulfurization tower spray layer (45) and a secondary desulfurization tower tail gas outlet (46) from bottom to top, a secondary desulfurization tower air inlet (47) is further arranged between the secondary desulfurization tower liquid storage tank (43) and the secondary desulfurization tower spray layer (45), the secondary desulfurization tower spray layer (45) is connected with the limestone absorbent slurry tank (42) through a pipeline, and the secondary desulfurization tower liquid storage tank (43) is connected with the gypsum sulfuric acid byproduct cement production device (8) through a pipeline.
8. The device according to claim 1, characterized in that the demister (5) is a two-stage wet electric demister connected in series.
CN202020250875.8U 2020-03-04 2020-03-04 Device of minimum emission of gypsum system sulphuric acid byproduct cement device tail gas Active CN211886185U (en)

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