CN113289467B - Treatment method of flue gas produced by metal catalyst - Google Patents
Treatment method of flue gas produced by metal catalyst Download PDFInfo
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- CN113289467B CN113289467B CN202110725734.6A CN202110725734A CN113289467B CN 113289467 B CN113289467 B CN 113289467B CN 202110725734 A CN202110725734 A CN 202110725734A CN 113289467 B CN113289467 B CN 113289467B
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 239000003546 flue gas Substances 0.000 title claims abstract description 133
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 122
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 33
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000001590 oxidative effect Effects 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 abstract description 10
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- 238000001354 calcination Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002918 waste heat Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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- 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
- B01D53/1431—Pretreatment by other processes
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- 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
- B01D53/1456—Removing acid components
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- 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
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/346—Controlling the process
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
The invention discloses a treatment method of flue gas produced by a metal catalyst, wherein the flue gas comprises first flue gas generated by a metal melting reaction and third flue gas generated by a calcining reaction of second flue gas generated by a decomposition reaction, and the treatment method comprises the following steps: (1) mixing the first flue gas and the second flue gas to obtain a first mixed gas; (2) oxidizing the first mixed gas to oxidize NO in the first mixed gas into NO 2 To obtain oxidized gas; (3) absorbing the oxidizing gas to obtain nitric acid and first tail gas; (4) mixing the first tail gas, the third flue gas and an ammonia source to obtain a second mixed gas; (3) carrying out denitration treatment on the second mixed gas to obtain nitrogen oxide with the concentration less than or equal to 200mg/m 3 Of the second exhaust gas. The treatment method of the flue gas produced by the metal catalyst not only is a process, but also perfectly utilizes the gradient of the waste heat of the flue gas in each section, and has low equipment investment and operation cost and high economic benefit.
Description
Technical Field
The invention relates to the technical field of treatment of flue gas produced by a metal catalyst, in particular to a treatment method of flue gas produced by the metal catalyst.
Background
The production process of the metal catalyst mainly comprises the steps of dissolving metal in nitric acid with medium concentration to obtain a nitrate solution, carrying out reduced pressure evaporation and cooling to obtain nitrate crystals, heating and decomposing the nitrate crystals to obtain metal oxide, and finally carrying out high-temperature calcination to obtain the metal catalyst. Therefore, the whole process of metal catalyst production mainly comprises three sections: a metal melting section, a decomposition section and a calcination section.
The three stages, although different in reactants and products, all produce nitrogen oxide gases, of which:
in the metal melting working section, nitric acid with the concentration of about 60% is generally adopted as a reactant to react with metal, and the generated flue gas is high-purity nitrogen oxide gas, but the gas flow is small and the temperature is low;
the decomposition section generally adopts electric heating continuous decomposition, the decomposition temperature is about 300-400 ℃, the generated flue gas is a mixed gas of nitrogen oxide gas and air, but the concentration of the nitrogen oxide is higher, and the gas temperature is higher;
the calcining section usually uses natural gas combustion as a heat source, the combustion temperature is about 1200-1500 ℃, the content of nitrogen oxides in the generated flue gas is obviously lower than that of flue gas in a metal melting section and flue gas in a decomposition section, the recovery value is low, but the temperature is higher, and the gas flow is larger.
Because the flue gas produced in the three sections has obvious difference in concentration and temperature, the current flue gas treatment mode is independent treatment, the efficiency is low, and the economic benefit is poor.
Disclosure of Invention
The invention aims to provide a treatment method and a treatment system for integrally treating three kinds of flue gas by comprehensively utilizing the attributes of the three sections of flue gas so as to reduce the treatment cost and efficiency of the flue gas produced by a metal catalyst and fully recover nitric oxide resources.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for treating a metal catalyst production flue gas. The technical scheme is as follows:
the treatment method of the flue gas produced by the metal catalyst comprises the following steps of:
(1) mixing the first flue gas and the second flue gas to obtain a first mixed gas;
(2) oxidizing the first mixed gas to oxidize NO in the first mixed gas into NO 2 Obtaining oxidized gas;
(3) absorbing the oxidizing gas to obtain nitric acid and first tail gas;
(4) mixing the first tail gas, the third flue gas and an ammonia source to obtain a second mixed gas;
(3) carrying out denitration treatment on the second mixed gas to obtain nitrogen oxide with the concentration less than or equal to 200mg/m 3 Of the second exhaust gas.
Further, the temperature of the first flue gas is 35-45 ℃; the temperature of the second flue gas is 185-215 ℃, and the concentration of nitrogen oxides is 26-34 g/m 3 (ii) a The temperature of the third flue gas is 185-215 ℃, and the concentration of nitrogen oxides is 160-240 mg/m 3 。
Further, the temperature of the first mixed gas is 180-210 ℃; the temperature of the oxidizing gas is 100-150 ℃; the temperature of the first tail gas is 35-45 ℃.
Furthermore, the temperature of any of the first mixed gas, the oxidizing gas and the first tail gas is monitored, and the flow of the first flue gas and/or the second flue gas is adjusted in real time according to the monitored values.
Further, the temperature of the second mixed gas is 100-200 ℃.
And further, monitoring the temperature of the second mixed gas, and adjusting the flow of the first tail gas and/or the third flue gas in real time according to the monitored value.
Furthermore, dilute nitric acid with the concentration of 5-15% is adopted to absorb the oxidizing gas, and the obtained nitric acid can be reused for the metallization reaction.
Further, the denitration treatment is low-temperature SCR denitration treatment, the ammonia source is ammonia gas, and the ammonia gas concentration is 2-10%.
Further, the volume ratio of the ammonia gas to the nitrogen oxides in the second mixed gas is (0.9-1.05): 1.
further, the metal catalyst is any one of nickel, zinc, copper, manganese, silver, lead, platinum and palladium.
In order to achieve the above object, according to another aspect of the present invention, there is also provided a treatment system for a metal catalyst production flue gas. The technical scheme is as follows:
the treatment system of metal catalyst production flue gas, the flue gas includes the first flue gas of metaplasia workshop section output, the second flue gas of decomposition workshop section output and the third flue gas of calcination workshop section output, and treatment system includes:
the first mixing unit is used for mixing the first flue gas and the second flue gas and outputting a first mixed gas;
an oxidation unit for oxidizing NO in the first mixed gas into NO 2 And outputting the oxidized gas;
the absorption unit is used for absorbing the nitric oxides in the oxidizing gas and outputting nitric acid and first tail gas;
the second mixing unit is used for mixing the first tail gas, the third flue gas and the ammonia source and outputting a second mixed gas;
the denitration unit is used for carrying out denitration output on the second mixed gas and outputting second tail gas;
and the temperature control unit comprises a first temperature control component for controlling the temperature of the first mixed gas and/or a second temperature control component for controlling the temperature of the second mixed gas.
Further, the first mixing unit comprises a first flue gas conveying pipeline, a second flue gas conveying pipeline and a first mixing tower.
Further, the first temperature control assembly comprises a first temperature sensor arranged on the first mixed gas conveying pipeline, a first controller, a first valve arranged on the first flue gas conveying pipeline and a second valve arranged on the second flue gas conveying pipeline.
Further, the oxidation unit comprises a first mixed gas conveying pipeline, an oxidant conveying pipeline and an oxidation tower; the absorption unit comprises an oxidizing gas conveying pipeline, an absorbent conveying pipeline and a spray tower.
Further, the second mixing unit comprises an ammonia injection grid, a first tail gas conveying pipeline, a third flue gas conveying pipeline and a second mixing tower.
Further, the second temperature control assembly comprises a second temperature sensor arranged on the second mixed gas conveying pipeline, a second controller, a third valve arranged on the first tail gas conveying pipeline and a fourth valve arranged on the third flue gas conveying pipeline.
Further, the denitration unit comprises a second mixer conveying pipeline and a low-temperature SCR denitration tower.
Further, the treatment system also comprises a nitric acid conveying unit, wherein the nitric acid conveying unit comprises a first nitric acid conveying pipeline and an intermediate tank which are connected with the absorption unit.
Further, the treatment system also comprises a nitric acid recycling unit, wherein the nitric acid recycling unit comprises a second nitric acid conveying pipeline arranged between the intermediate tank and the metal melting working section; and/or a liquid level meter is arranged in the intermediate tank.
Furthermore, the second nitric acid conveying pipeline comprises a header pipe, a three-way valve, a first branch pipe and a second branch pipe, wherein a pH sensor is arranged on the header pipe, and a concentration device is arranged on the second branch pipe.
It can be seen that the treatment method and the treatment system for the flue gas produced by the metal catalyst have the following advantages:
firstly, the gas quantity, the temperature and the concentration of the flue gas in three sections are fully considered, and only the first flue gas and the second flue gas are subjected to integrated treatment, so that the temperature requirement of oxidation absorption is met, and nitrogen oxide resources are fully recovered;
secondly, the lower temperature of the first tail gas generated after oxidation and absorption and the higher temperature of the third flue gas are fully utilized to meet the reaction temperature required by rear-end denitration, and the standard-reaching emission of nitrogen oxide is realized on the basis of no additional energy;
meanwhile, the first flue gas and the second flue gas with higher nitrogen oxide purity are subjected to oxidation absorption treatment, so that the purity of the nitric acid is ensured, the requirement of reusing the nitric acid in a metal melting section is met, and the raw material cost is saved;
therefore, the treatment method and the treatment system for the flue gas produced by the metal catalyst have the advantages of simple process and structure, perfect utilization of the gradient of the waste heat of the flue gas in each section, low equipment investment and operation cost and high economic benefit.
The invention is further described with reference to the following figures and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to assist in understanding the invention, and are included to explain the invention and their equivalents and not limit it unduly. In the drawings:
fig. 1 is a schematic structural diagram of a first embodiment of the treatment system for flue gas produced by metal catalyst of the present invention.
Fig. 2 is a schematic structural diagram of a second embodiment of the treatment system for flue gas produced by metal catalyst of the present invention.
Fig. 3 is a schematic structural diagram of a third embodiment of the treatment system for flue gas produced by metal catalyst of the present invention.
Fig. 4 is a schematic structural diagram of a fourth embodiment of the treatment system for flue gas produced by metal catalyst of the present invention.
The relevant references in the above figures are:
the method comprises the following steps of 110-metallizing section, 120-decomposing section, 130-calcining section, 210-first mixing unit, 300-oxidizing unit, 400-absorbing unit, 220-second mixing unit, 510-first temperature sensor, 520-first valve, 530-second valve, 600-denitration unit, 700-nitric acid conveying unit, 810-second temperature sensor, 820-third valve, 830-fourth valve, 910-three-way valve and 920-concentrating device.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is described in detail with reference to the accompanying drawings, it is to be noted that:
the technical solutions and features provided in the present invention in each part including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions.
In the following embodiments, the metal catalyst is any one of nickel, zinc, copper, manganese, silver, lead, platinum and palladium, the flue gas produced by the metal catalyst includes a first flue gas produced by a chemical metal reaction and a second flue gas produced by a decomposition reaction, and a third flue gas produced by a calcination reaction, and the flue gas treatment method is preferably, but not limited to, the following four embodiments respectively:
the treatment method for the flue gas produced by the metal catalyst comprises the following steps:
(1) mixing the first flue gas and the second flue gas to obtain a first mixed gas;
(2) oxidizing the first mixed gas to oxidize NO in the first mixed gas into NO by oxygen 2 Obtaining oxidized gas;
(3) absorbing the oxidizing gas to obtain nitric acid and first tail gas;
(4) mixing the first tail gas, the third flue gas and an ammonia source to obtain a second mixed gas;
(3) carrying out denitration treatment on the second mixed gas to obtain nitrogen oxide with the concentration less than or equal to 200mg/m 3 Of the second exhaust gas.
Wherein the temperature of the first flue gas is 35-45 ℃; the temperature of the second flue gas is 185-215 ℃, and the concentration of nitrogen oxides is 26-34 g/m 3 (ii) a The temperature of the third flue gas is 185-215 ℃, and the concentration of nitrogen oxides is 160-240 mg/m 3 . Therefore, the degree of fit between the temperature and the concentration of the first flue gas, the second flue gas and the third flue gas and the process is higher, and the operation is more stable.
The temperature of the first mixed gas is 180-210 ℃; the temperature of the oxidizing gas is 100-150 ℃; the temperature of the first tail gas is 35-45 ℃. Therefore, the efficiency of oxidant absorption is high, and the temperatures of the first flue gas and the second flue gas are fully utilized.
The temperature of the second mixed gas is 100-200 ℃, and preferably 120-180 ℃. Therefore, the denitration efficiency is high, and the temperatures of the first tail gas and the third flue gas are fully utilized.
And (3) absorbing the oxidizing gas by using dilute nitric acid with the concentration of 5-15%, wherein the obtained nitric acid can be reused for the metallization reaction. When the concentration of the dilute nitric acid is 8-12%, the absorption effect is best.
The denitration treatment is low-temperature SCR denitration treatment, the ammonia source is ammonia gas, the concentration of the ammonia gas is 2-10%, and the volume ratio of the ammonia gas to the nitric oxide in the second mixed gas is (0.9-1.05): 1; therefore, nitrogen oxide and ammonia gas in the second mixed gas react to generate nitrogen gas and water under the low-temperature catalysis of the SCR denitration catalyst, the temperature gradient change is fully utilized, the denitration rate is high, and the concentration of the nitrogen oxide in the second tail gas can be controlled to be less than or equal to 200mg/m 3 。
On the basis of the first embodiment, the treatment method for the metal catalyst production flue gas of the second embodiment further comprises the following steps: the temperature of any of the first mixed gas, the oxidizing gas and the first tail gas is monitored, and the flow of the first flue gas and/or the second flue gas is adjusted in real time according to the monitored values.
Therefore, the flow of the first flue gas and/or the second flue gas is adjusted in real time, the optimal oxidation treatment temperature and the optimal absorption treatment temperature are ensured to be met, and the recovery rate of the nitrogen oxides is improved.
On the basis of the first embodiment, the treatment method for the metal catalyst production flue gas of the third embodiment further comprises the following steps: and monitoring the temperature of the second mixed gas, and adjusting the flow of the first tail gas and/or the third flue gas in real time according to the monitored value.
From this, through adjusting the flow of first tail gas and/or third flue gas in real time, ensure to satisfy best denitration temperature, promote the denitration rate.
The method for treating flue gas produced by using a metal catalyst according to the fourth embodiment is a combination of the second and third embodiments, and thus the recovery rate of nitrogen oxides and the denitration rate can be sufficiently ensured.
The treatment system for the flue gas produced by the metal catalyst, which is composed of the first flue gas output from the metal melting section 110, the second flue gas output from the decomposition section 120 and the third flue gas output from the calcination section 130, is preferably, but not limited to, the following four specific embodiments, respectively:
fig. 1 is a schematic structural diagram of a first embodiment of the treatment system for flue gas produced by metal catalyst of the present invention.
As shown in fig. 1, the treatment system for flue gas produced by metal catalyst comprises a first mixing unit 210, an oxidation unit 300, an absorption unit 400, a second mixing unit 220, a denitration unit 600, a temperature control unit, and a nitric acid conveying unit 700; wherein,
the first mixing unit 210 is configured to mix the first flue gas and the second flue gas and output a first mixed gas; the first mixing unit 210 includes a first flue gas conveying pipeline, a second flue gas conveying pipeline, and a first mixing tower.
The oxidation unit 300 is used for oxidizing NO in the first mixed gas into NO 2 And outputting the oxidized gas; the oxidation unit 300 includes a first mixture gas delivery pipe, an oxidant delivery pipe for delivering oxygen, and an oxidation towerAnd (5) qi.
The absorption unit 400 is used for absorbing nitrogen oxides in the oxidizing gas and outputting nitric acid and first tail gas; the absorption unit 400 comprises an oxidizing gas conveying pipeline, an absorbent conveying pipeline and a spray tower, wherein the oxidizing gas flows in the spray tower from bottom to top, and the absorbent is in countercurrent contact with the oxidizing gas in the spray tower from top to bottom under the action of a pump.
The second mixing unit 220 is configured to mix the first tail gas, the third flue gas, and the ammonia source and output a second mixed gas; the second mixing unit 220 includes an ammonia injection grid, a first tail gas delivery pipeline, a third flue gas delivery pipeline, and a second mixing tower.
The denitration unit 600 is configured to perform denitration on the second mixed gas and output a second tail gas; the denitration unit 600 includes a second mixer delivery pipe and a low-temperature SCR denitration tower.
The temperature control unit comprises a first temperature control component for controlling the temperature of the first mixed gas; the first temperature control assembly comprises a first temperature sensor 510 arranged on a first mixed gas conveying pipeline, a first controller, a first valve 520 arranged on a first flue gas conveying pipeline and a second valve 530 arranged on a second flue gas conveying pipeline, and the first controller adjusts the opening and closing degree of the first valve 520 and the second valve 530 in real time according to the detection value of the first temperature sensor 510.
The nitric acid conveying unit 700 comprises a first nitric acid conveying pipeline connected with the absorption unit 400 and a middle tank, and a liquid level meter is arranged in the middle tank.
Fig. 2 is a schematic structural diagram of a second embodiment of the treatment system for flue gas produced by metal catalyst of the present invention.
The second embodiment of the metal catalyst production flue gas treatment system has the differences compared to the first embodiment: as shown in fig. 2, the temperature control unit includes a second temperature control component for controlling the temperature of the second mixed gas, the second temperature control component includes a second temperature sensor 810 disposed on the second mixed gas conveying pipeline, a second controller, a third valve 820 disposed on the first tail gas conveying pipeline, and a fourth valve 830 disposed on the third flue gas conveying pipeline, and the second controller adjusts the opening and closing degrees of the third valve 820 and the fourth valve 830 in real time according to the detection value of the second temperature sensor 810.
Fig. 3 is a schematic structural diagram of a third embodiment of the treatment system for flue gas produced by metal catalyst of the present invention.
As shown in fig. 3, the treatment system for flue gas produced by using a metal catalyst according to the third embodiment is a combination of the second and third embodiments, so that the recovery rate of nitrogen oxides and the denitration rate can be sufficiently ensured. In this case, the first controller and the second controller may be replaced by one overall controller.
Fig. 4 is a schematic structural diagram of a fourth embodiment of the treatment system for flue gas produced by metal catalyst of the present invention.
The fourth embodiment of the metal catalyst production flue gas treatment system further has, as compared with the third embodiment: as shown in fig. 4, the system further comprises a nitric acid recycling unit, wherein the nitric acid recycling unit comprises a second nitric acid conveying pipeline arranged between the intermediate tank and the metal melting section 110.
The second nitric acid conveying pipeline comprises a header pipe, a three-way valve 910, a first branch pipe and a second branch pipe, a pH sensor is arranged on the header pipe, and a concentration device 920 is arranged on the second branch pipe, so that when the concentration of the nitric acid in the intermediate tank does not meet the requirement of the metal melting reaction, the nitric acid can be concentrated to the required concentration through the concentration device 920 and then conveyed to the metal melting working section 110 through the second branch pipe.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.
Claims (10)
1. The treatment method of the flue gas produced by the metal catalyst comprises the steps of gasifying first flue gas produced by metal reaction and decomposing second flue gas produced by metal reaction to calcine third flue gas produced by the metal reaction, and is characterized in that: the processing method comprises the following steps:
(1) mixing the first flue gas and the second flue gas to obtain a first mixed gas;
(2) oxidizing the first mixed gas to oxidize NO in the first mixed gas into NO 2 Obtaining oxidized gas;
(3) absorbing the oxidizing gas to obtain nitric acid and first tail gas;
(4) mixing the first tail gas, the third flue gas and an ammonia source to obtain a second mixed gas;
(5) carrying out denitration treatment on the second mixed gas to obtain nitrogen oxide with the concentration less than or equal to 200mg/m 3 Of the second exhaust gas.
2. The method for treating flue gas generated in the production of metal catalysts according to claim 1, wherein the method comprises the following steps: the temperature of the first flue gas is 35-45 ℃; the temperature of the second flue gas is 185-215 ℃, and the concentration of nitrogen oxides is 26-34 g/m 3 (ii) a The temperature of the third flue gas is 185-215 ℃, and the concentration of nitrogen oxides is 160-240 mg/m 3 。
3. The method for treating flue gas generated in the production of metal catalysts according to claim 2, wherein the method comprises the following steps: the temperature of the first mixed gas is 180-210 ℃; the temperature of the oxidizing gas is 100-150 ℃; the temperature of the first tail gas is 35-45 ℃.
4. The method for treating flue gas generated in the production of metal catalysts according to claim 3, wherein the method comprises the following steps: the temperature of any of the first mixed gas, the oxidizing gas and the first tail gas is monitored, and the flow of the first flue gas and/or the second flue gas is adjusted in real time according to the monitored values.
5. The method for treating flue gas generated in the production of metal catalysts according to claim 2, wherein the method comprises the following steps: the temperature of the second mixed gas is 100-200 ℃.
6. The method for treating flue gas generated in the production of metal catalysts according to claim 5, wherein the method comprises the following steps: and monitoring the temperature of the second mixed gas, and adjusting the flow of the first tail gas and/or the third flue gas in real time according to the monitored value.
7. The method for treating flue gas generated in the production of metal catalysts according to claim 1, wherein the method comprises the following steps: and (3) absorbing the oxidizing gas by using dilute nitric acid with the concentration of 5-15%, and reusing the obtained nitric acid for a metal-melting reaction.
8. The method for treating flue gas generated in the production of metal catalysts according to claim 1, wherein the method comprises the following steps: the denitration treatment is low-temperature SCR denitration treatment, the ammonia source is ammonia gas, and the concentration of the ammonia gas is 2-10%.
9. The method for treating flue gas generated in the production of metal catalysts according to claim 8, wherein the method comprises the following steps: the volume ratio of ammonia to nitrogen oxide in the second mixed gas is (0.9-1.05): 1.
10. the method for treating flue gas generated in the production of metal catalysts according to claim 1, wherein the method comprises the following steps: the metal catalyst is any one of nickel, zinc, copper, manganese, silver, lead, platinum and palladium.
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