CN113660996A - Acidic exhaust gas treatment agent, acidic exhaust gas treatment method, and acidic exhaust gas treatment device - Google Patents
Acidic exhaust gas treatment agent, acidic exhaust gas treatment method, and acidic exhaust gas treatment device Download PDFInfo
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- 230000002378 acidificating effect Effects 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 85
- 229910003023 Mg-Al Inorganic materials 0.000 claims abstract description 70
- 239000000126 substance Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 15
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 39
- 239000011572 manganese Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 121
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 50
- 238000002485 combustion reaction Methods 0.000 abstract description 9
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910018663 Mn O Inorganic materials 0.000 description 4
- 229910003176 Mn-O Inorganic materials 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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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
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Treating Waste Gases (AREA)
- Separation Of Gases By Adsorption (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
Providing: an acidic exhaust gas treating agent, an acidic exhaust gas treating method, and an acidic exhaust gas treating facility, which can improve the removal efficiency of nitric oxide compared to conventional acidic exhaust gas treating agents, acidic exhaust gas treating methods, and acidic exhaust gas treating facilities, when treating acidic exhaust gas generated from combustion facilities such as thermal power plants and incineration facilities using a layered double hydroxide. The acidic waste gas treatment method of the present invention comprises the following steps: a step (1) in which an acidic exhaust gas treatment agent, which is a composite product of manganese oxide and at least one of permanganic acid compounds and contains a Mg-Al-based layered double hydroxide, is used, the acidic exhaust gas is brought into contact with the acidic exhaust gas treatment agent, and acidic substances in the acidic exhaust gas are adsorbed; a step (2) of desorbing the acidic substance adsorbed to the acidic exhaust gas treating agent in the step (1) to regenerate the acidic exhaust gas treating agent; and a step (3) of recovering the acidic substance desorbed from the acidic exhaust gas treating agent in the step (2).
Description
Technical Field
The present invention relates to: an acidic exhaust gas treating agent, an acidic exhaust gas treating method, and an acidic exhaust gas treating facility, which are suitable for treating acidic exhaust gas generated from combustion facilities such as thermal power plants and incineration facilities.
Background
Combustion exhaust gas generated by thermal power generation, waste incineration, or the like contains harmful acidic substances such as hydrogen chloride, sulfur oxides, nitrogen oxides, and the like. Therefore, for the acidic exhaust gas containing the aforementioned acidic substance, treatment for removing the aforementioned acidic substance is performed based on various methods.
Among the acidic substances, hydrogen chloride and sulfur oxides are widely treated as follows: the treatment is carried out by a dry method in which the product is neutralized with an alkaline agent such as hydrated lime and collected by a dust collector, or a wet method in which the product is neutralized with a scrubber.
In addition, for nitrogen oxides, treatment by a selective catalytic reduction method (SCR) in which a reducing agent such as ammonia or urea is mixed with combustion exhaust gas and then decomposed into nitrogen gas and water by a catalyst in which vanadium, platinum, or the like is supported on a carrier such as ceramics, and treatment by a non-catalytic reduction method (SNCR) in which nitrogen oxides are decomposed by directly spraying a reducing agent such as ammonia or urea into an incinerator or the like have been widely used.
However, the above treatment by neutralization requires a treatment step of neutralizing the product, and further requires a separate treatment of nitrogen oxide.
Further, the treatment of nitrogen oxides by SCR and SNCR requires the use of a reducing agent, a catalyst, and the like, and requires equipment, energy, and other costs therefor.
To solve such problems, the present inventors have proposed the following: the acidic exhaust gas can be treated efficiently and at a lower cost by using a carbonic acid type Mg — Al layered double hydroxide (see patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-190199
Disclosure of Invention
Problems to be solved by the invention
However, even when the treatment method described in patent document 1 is used, the treatment for removing nitric oxide may not necessarily be sufficient.
Therefore, in the treatment of acidic exhaust gas using a layered double hydroxide, it is required to improve the efficiency of removing nitric oxide.
The present invention has been made under such circumstances, and an object thereof is to provide: an acidic exhaust gas treating agent, an acidic exhaust gas treating method, and an acidic exhaust gas treating facility, which can improve the removal efficiency of nitric oxide compared to conventional acidic exhaust gas treating agents, acidic exhaust gas treating methods, and acidic exhaust gas treating facilities, when treating acidic exhaust gas generated from combustion facilities such as thermal power plants and incineration facilities using a layered double hydroxide.
Means for solving the problems
The present invention is based on the following findings: a composite material based on manganese oxide or the like of Mg — Al Layered Double Hydroxide (hereinafter also referred to as Mg — Al LDH (Layered Double Hydroxide)) has excellent nitric oxide removing performance.
Namely, the present invention provides the following [1] to [7 ].
[1] An acidic exhaust gas treatment agent comprising a composite of a Mg-Al-based layered double hydroxide based on at least either one of a manganese oxide and a permanganate compound.
[2] The acidic exhaust gas treating agent according to the above [1], wherein the complex compound is at least one of manganese dioxide complex Mg-Al-based layered double hydroxide and high manganese acid Mg-Al-based layered double hydroxide.
[3] The acidic exhaust gas treating agent according to the above [1] or [2], which comprises a carbonic acid type Mg-Al based layered double hydroxide.
[4] A method for treating an acidic exhaust gas by using the acidic exhaust gas treating agent according to any one of the above [1] to [3], the method comprising: a step (1) of bringing the acidic exhaust gas into contact with the acidic exhaust gas treatment agent and adsorbing acidic substances in the acidic exhaust gas; a step (2) of desorbing the acidic substance adsorbed to the acidic exhaust gas treating agent in the step (1) to regenerate the acidic exhaust gas treating agent; and a step (3) of recovering the acidic substance desorbed from the acidic exhaust gas treating agent in the step (2).
[5] The acidic exhaust gas treatment method according to the above [4], wherein the treatment cycle comprising the above steps (1) to (3) is repeated, and in the step (1) of at least any one of the treatment cycles 2 nd and thereafter of the above treatment cycle, the acidic exhaust gas treatment agent regenerated in the step (2) of at least any one of the treatment cycles before the treatment cycle is used as at least a part of the acidic exhaust gas treatment agent.
[6] An acidic exhaust gas treatment facility for treating an acidic exhaust gas with the acidic exhaust gas treatment agent according to any one of the above [1] to [3], the treatment facility comprising: an apparatus (1) for bringing the acidic exhaust gas into contact with the acidic exhaust gas treatment agent and adsorbing acidic substances in the acidic exhaust gas; a device (2) for desorbing the acidic substance adsorbed to the acidic exhaust gas treating agent in the device (1) to regenerate the acidic exhaust gas treating agent; and a device (3) for recovering the acidic substance desorbed from the acidic exhaust gas treating agent in the device (2).
[7] The acidic exhaust gas treatment method according to the above [4], wherein the manganese dioxide composite Mg-Al based layered double hydroxide is produced by a production method which does not require a reduction step, and the manganese dioxide composite Mg-Al based layered double hydroxide is produced by adding a Mg-Al oxide to an aqueous potassium permanganate solution, filtering the precipitate, and drying the filtered precipitate.
ADVANTAGEOUS EFFECTS OF INVENTION
By using the acidic exhaust gas treating agent of the present invention, it is possible to simultaneously remove acidic exhaust gases such as hydrogen chloride, sulfur oxides, and nitrogen oxides generated from combustion facilities such as a thermal power plant and an incineration facility, and in particular, the removal efficiency of nitrogen monoxide is improved as compared with the case of using a conventional layered double hydroxide.
In addition, according to the acidic exhaust gas treatment method of the present invention using the acidic exhaust gas treatment agent, acidic exhaust gas can be effectively removed with a smaller treatment amount than in the conventional method, and the acidic exhaust gas treatment agent can be regenerated and used.
Further, according to the acid exhaust gas treatment device of the present invention, the acid exhaust gas treatment method can be suitably performed, and the acid exhaust gas can be treated more efficiently and at lower cost than in the past.
Drawings
FIG. 1 shows NO of reaction tube outlet gas in the test for evaluating the acid exhaust gas treating performance of the examplexGraph of the temporal change in concentration.
FIG. 2 is a powder X-ray diffraction pattern of the product of Synthesis example 1.
FIG. 3 is a powder X-ray diffraction pattern of the product of Synthesis example 2.
FIG. 4 is CO3Powder X-ray diffraction pattern of form Mg-Al LDH.
FIG. 5 is an XPS spectrum of the product of Synthesis example 1.
FIG. 6 is an XPS spectrum of the product of Synthesis example 2.
Detailed Description
The acidic exhaust gas treating agent, and the acidic exhaust gas treating method and the acidic exhaust gas treating facility using the same according to the present invention will be described in detail below.
[ acidic exhaust gas treating agent ]
The acidic exhaust gas treatment agent of the present invention comprises a complex of Mg-Al LDH based on at least either one of a manganese oxide and a permanganate compound (hereinafter also referred to as Mn-O compound).
By using Mg-Al LDH as a composite of manganese and oxygen-based compounds (Mn-O compounds) as the acidic exhaust gas treating agent in this manner, the efficiency of removing nitrogen monoxide can be improved as compared with the case of using conventional Mg-Al LDH as a layered double hydroxide, or the like.
This is presumably because: although Mg-Al LDH itself does not readily adsorb nitrogen monoxide, nitrogen monoxide is oxidized to nitrogen dioxide by the catalytic action of the complexed Mn-O compound, and further, is easily oxidized to nitrate ions, and is easily adsorbed to the complex of Mg-Al LDH.
Manganese may have an oxidation number of +2 to +7, but from the viewpoint of its action as an oxidation catalyst, a larger oxidation number is preferred. From the viewpoint of ease of synthesis and the like, the composite compound is preferably, for example: manganese dioxide based on manganese with an oxidation number of +4, composite Mg-Al layered double hydroxide (hereinafter also referred to as MnO)2Compounding Mg-Al LDH. ) Or a high manganese acid type Mg-Al based layered double hydroxide (hereinafter also referred to as MnO) based on manganese having an oxidation number of +74Type Mg-Al LDH. ) And the like. The complex may contain 1 kind of compound alone or 2 or more kinds of compound.
MnO2The structural formula of the composite Mg-Al LDH is represented by the following formula (1), and MnO is added4The structural formula of the Mg-Al LDH is represented by the following formula (2).
Mg1-xAlx(OH)2(MnO2)2.5x(Cl)x·mH2O (1)
Mg1-xAlx(OH)2(MnO4)x·mH2O (2)
In the formulae (1) and (2), x is usually 0.20 to 0.40, and m is usually 1 to 12.
The acidic exhaust gas treating agent preferably contains a carbonic acid type Mg-Al layered double hydroxide (hereinafter also referred to as CO)3Type Mg-Al LDH. ).
As described in patent document 1, CO3The Mg — Al LDH is a compound that can be suitably used for treatment of acidic exhaust gas, and can effectively remove acidic compounds other than nitrogen monoxide, such as hydrogen chloride, sulfur dioxide, and nitrogen dioxide, contained in acidic exhaust gas. Therefore, it is preferably used in combination with the above-mentioned complex compound.
In this case, the complex compound and CO in the acidic exhaust gas treating agent3Type Mg-AlThe content ratio of LDH is not particularly limited, and may be appropriately set according to the composition of the acidic exhaust gas, such as the amount of nitric oxide contained in the acidic exhaust gas to be treated.
CO3The Mg — Al LDH type is also present as hydrotalcite in naturally occurring clay minerals, but when it is synthesized, the synthesis method is not particularly limited, and a known method can be used (for example, the method described in patent document 1).
For example, magnesium nitrate (Mg (NO) is mixed with Mg/Al 2/1 (molar ratio) at the same time3)2) And aluminum nitrate (Al (NO)3)3) While maintaining the pH at 10.5, the aqueous solution of (A) was added dropwise to sodium carbonate (Na)2CO3) In an aqueous solution, thereby obtaining the product. Specifically, the synthesis can be carried out by the method shown in the following examples.
In addition, MnO2Composite Mg-Al LDH and MnO4The method for synthesizing the Mg-Al LDH is not particularly limited, and CO may be used3The Mg-Al LDH form is used as a raw material compound and is synthesized by utilizing an anion exchange function based on its intercalation.
For example, CO is introduced at 500 ℃3Pre-roasting the Mg-Al LDH to obtain Mg-Al oxide, and adding potassium permanganate (KMnO)4) By mixing in an aqueous solution, permanganate ions (MnO) can be synthesized and trapped4 -) MnO of4Type Mg-Al LDH.
Further, MnO4Type Mg-Al LDH in potassium permanganate (KMnO)4) In aqueous solution to MnO2Compounding Mg-Al LDH.
In addition, by adding MnO described above4Type Mg-Al LDH added to manganese chloride (MnCl)2) In an aqueous solution and mixed to thereby enable synthesis of MnO2Compounding Mg-Al LDH.
The acidic exhaust gas treating agent may contain agents other than layered double hydroxides such as calcium hydroxide (slaked lime), calcium oxide, sodium bicarbonate (sodium bicarbonate), sodium carbonate, dolomite hydroxide, dolomite lighter than calcined, aluminum hydroxide, aluminum oxide, magnesium hydroxide, and magnesium oxide, as long as the effects of the present invention are not impaired. However, in the acidic exhaust gas treatment method described later, when the acidic exhaust gas treatment agent is regenerated and supplied for reuse, it is preferable not to include such an agent from the viewpoint of the purity of the regenerated product, the recovery operation, and the like.
[ method of treating acidic exhaust gas ]
The method for treating acidic exhaust gas by using the acidic exhaust gas treating agent is not particularly limited, and the acidic exhaust gas treating agent (hereinafter also simply referred to as treating agent) is preferably used in the acidic exhaust gas treating method of the present invention.
The acidic waste gas treatment method of the present invention comprises the following steps: a step (1) of bringing an acidic exhaust gas into contact with the treating agent and adsorbing an acidic substance in the acidic exhaust gas; a step (2) of desorbing the acidic substance adsorbed on the treating agent in the step (1) to regenerate the treating agent; and a step (3) of recovering the acidic substance desorbed from the treating agent in the step (2).
According to the above-mentioned treatment method, the regenerated treatment agent can be reused. The acidic substance is dissolved in water and recovered as an acid (aqueous solution), for example, and the acid can be used for industrial purposes and the like.
In the step (1), nitric oxide is oxidized by the composite compound in the treating agent, and the acidic substance in the acidic exhaust gas is adsorbed on the treating agent by anion exchange or the like involving the interlayer of the layered double hydroxide.
Next, in the step (2), the acidic substance adsorbed on the treatment agent is desorbed from the treatment agent by reversible anion exchange or the like. The anion exchange in this case can be, for example, with CO3Type Mg-Al LDH, MnO2Composite Mg-Al LDH and MnO4The synthesis of Mg — Al LDH can be carried out by mixing and stirring various aqueous solutions in the same manner, and thus the treatment agent can be easily regenerated.
The treatment agent thus regenerated can be reused, and therefore the cost for treating the acidic exhaust gas can be reduced.
In the step (3), the acidic substance desorbed from the treating agent in the step (2) is recovered. For example, the acid (aqueous solution) can be recovered by dissolving in water, and the acid can be used for industrial use and the like.
As described above, the treatment method of the present invention is a method excellent in the recyclability not only for the treatment agent but also for the acidic exhaust gas to be treated.
Among the above-mentioned treatment methods, it is preferable that: the treatment cycle comprising the steps (1) to (3) is repeated, and in the step (1) of at least one of the 2 nd and subsequent treatment cycles of the treatment cycle, the treatment agent regenerated in the step (2) of at least one of the treatment cycles before the treatment cycle is used as at least a part of the treatment agent.
In this way, when the treatment method is repeatedly performed, the total amount of the treatment agent required for the treatment of the acidic exhaust gas can be reduced by reusing the treatment agent regenerated in the previous step, and the treatment cost of the acidic exhaust gas can be reduced.
The method for treating an acidic exhaust gas of the present invention as described above is excellent in working efficiency because it can remove various acidic substances in an acidic exhaust gas simultaneously with 1 treatment agent. In particular, by using the composite material as a treatment agent, the efficiency of removing nitric oxide can be improved compared with the conventional one.
Further, the treatment load of waste generated in the treatment can be reduced without generating a neutralized product.
[ acid exhaust gas treatment facility ]
The apparatus for treating acidic exhaust gas using the aforementioned acidic exhaust gas treating agent is not particularly limited, and the aforementioned treating agent is preferably applied to the acidic exhaust gas treating apparatus of the present invention.
The acidic exhaust gas treatment facility of the present invention comprises the following means: an apparatus (1) for bringing an acidic exhaust gas into contact with the treating agent and adsorbing an acidic substance in the acidic exhaust gas; a device (2) for desorbing the acidic substance adsorbed to the treating agent in the device (1) and regenerating the treating agent; and a device (3) for recovering the acidic substance desorbed from the treating agent in the device (2).
The device (1) may be configured by providing a flow path for acidic exhaust gas in a container containing the treatment agent, for example.
The apparatus (2) may be configured, for example, in such a manner that the treatment agent taken out from the vessel through which the acidic exhaust gas has flowed is mixed with the CO in the immersion tank3Type Mg-Al LDH, MnO2Composite Mg-Al LDH and MnO4The same method as the method for synthesizing the Mg-Al LDH is used, and the Mg-Al LDH is immersed in various aqueous solutions and mixed and stirred according to the chemical species for complexing with the Mg-Al LDH.
The device (3) may be configured as an aqueous solution storage tank that is dissolved in water and recovered as an acid (aqueous solution), for example.
The acidic exhaust gas treatment facility may be attached to a combustion facility in thermal power generation, waste incineration, or the like. For example, when treating acidic exhaust gas generated in a waste incinerator, the following configuration can be adopted: the acidic exhaust gas treatment facility is provided in succession to a boiler, an exhaust gas cooling device, and a dust collector, which are provided in this order in the combustion exhaust gas system of the incinerator body, and the treated exhaust gas from the acidic exhaust gas treatment facility is introduced into a chimney by a suction fan or the like and is released from the chimney into the atmosphere.
Examples
The present invention will be described in more detail below, but the present invention is not limited to the following examples.
Synthesis example 1]MnO2Synthesis of composite Mg-Al LDH
A mixed aqueous solution having a magnesium concentration of 0.33 mol/L and an aluminum concentration of 0.17 mol/L was prepared using magnesium nitrate hexahydrate and aluminum nitrate nonahydrate (magnesium/aluminum-2/1 (molar ratio)).
The mixed solution was added dropwise to an aqueous solution of sodium carbonate having a concentration of 0.1 mol/L at 30 ℃ while stirring. At this time, the pH was maintained at 10.5 by dropwise addition of a 1.25 mol/L aqueous solution of sodium hydroxide.
After the completion of the dropwise addition, the mixture was stirred at 30 ℃ for 1 hour. Then, the precipitate was filtered and washed repeatedly at 40 ℃ to 40 ℃Drying under reduced pressure for hours to obtain CO3Type Mg-Al LDH.
The obtained CO is3The type Mg-Al LDH is pre-roasted for 2 hours at 500 ℃, then is put into potassium permanganate aqueous solution with the concentration of 0.2 mol/L under nitrogen flow, and is stirred for 6 hours at 30 ℃. Then, the precipitate was filtered and washed repeatedly, and the product obtained by drying at 40 ℃ for 40 hours under reduced pressure was put into an aqueous solution of manganese chloride having a concentration of 0.1 mol/L under a nitrogen gas flow, and stirred at 30 ℃ for 3 hours. Then, the precipitate was filtered and washed repeatedly, and dried under reduced pressure at 40 ℃ to obtain MnO2Composite Mg-Al LDH (Mg)0.62Al0.38(OH)2(MnO2)0.95(Cl)0.38·1.13H2O)。
Synthesis example 2]MnO2Synthesis of composite Mg-Al LDH
A mixed aqueous solution having a magnesium concentration of 0.33 mol/L and an aluminum concentration of 0.17 mol/L was prepared using magnesium nitrate hexahydrate and aluminum nitrate nonahydrate (magnesium/aluminum-2/1 (molar ratio)).
The mixed solution was added dropwise to an aqueous solution of sodium carbonate having a concentration of 0.1 mol/L at 30 ℃ while stirring. At this time, the pH was maintained at 10.5 by dropwise addition of a 1.25 mol/L aqueous solution of sodium hydroxide.
After the completion of the dropwise addition, the mixture was stirred at 30 ℃ for 1 hour. Then, the precipitate was filtered and washed repeatedly, and dried at 40 ℃ for 40 hours under reduced pressure to obtain CO3Type Mg-Al LDH.
The obtained CO is3The type Mg-Al LDH is pre-roasted for 2 hours at 500 ℃, then is put into potassium permanganate aqueous solution with the concentration of 0.2 mol/L under nitrogen flow, and is stirred for 6 hours at 30 ℃. Then, the precipitate was filtered and washed repeatedly, and then dried at 40 ℃ for 40 hours under reduced pressure.
In addition, the identification of CO in Synthesis examples 1 and 2 was carried out by powder X-ray diffractometry (powder XRD)3Type Mg-Al LDH, MnO4Forms of Mg-Al LDH, and MnO2Compounding Mg-Al LDH. For CO3Form Mg-Al LDH, powder X-ray diffraction pattern is shown in FIG. 4. In addition, X-ray diffractometry was usedThe apparatus was designated as "RINT-2200 VHF" manufactured by Rigaku Corporation, and CuK α rays (1.5418A) were used as characteristic X-rays for measurement. Further, the Mn-O compound-based complex also shows the elemental analysis values by inductively coupled plasma emission spectrometry (ICP-AES). MnO in Synthesis examples 1 and 24Forms of Mg-Al LDH, and MnO2The composite Mg-Al LDH was identified by determining the oxidation number of Mn using X-ray photoelectron spectroscopy (XPS).
[ evaluation test of acid exhaust gas treatment Performance ]
(example 1)
MnO obtained in Synthesis example 12Composite Mg-Al LDH1.0g was filled in a glass wool in a reaction tube (inner diameter: 16mm) of a tubular electric furnace. The set temperature of the tubular electric furnace was set at 170 ℃ and the test gases (carrier gas: nitrogen, nitric oxide gas concentration 150volppm, oxygen gas concentration 10 vol%) were introduced into the reaction tube at a linear velocity of 1.0 m/min while adjusting the flow rate by a mass flow controller. Using a combustion exhaust gas analyser (Testo SE) based on potentiostatic electrolysis&Manufactured by kgaa) of the reaction tube was measured for NO in the outlet gasxThe concentration was changed with time (90 minutes).
Comparative example 1
In example 1, MnO was added2Change of composite Mg-Al LDH to CO obtained in Synthesis Process of Synthesis example 13Evaluation tests were carried out in the same manner as in example 1 except for the type of Mg — Al LDH.
FIG. 1 is a graph showing NO of outlet gases of reaction tubes in example 1 and comparative example 1xThe change in concentration with time.
In addition, by NOxThe cumulative concentration of the concentration was determined to determine the reaction rate of nitric oxide gas in the test gas, and as a result: 91.5 vol% for example 1 and 2.2 vol% for comparative example 1.
From these results it is clear that: composite material ratio CO of manganese dioxide and Mg-Al series layered double hydroxide3The type Mg-Al LDH has excellent nitric oxide removal performance.
[ MnO based on Synthesis examples 1 and 22Analysis of Presence ratio of composite Mg-Al LDH]
Powder X-ray diffraction patterns based on the products of synthesis examples 1 and 2 are shown in fig. 2 and 3. In addition, XPS spectra based on the products of synthesis examples 1 and 2 are shown in fig. 5 and 6.
From the elemental analysis values, the Mg/Al molar ratios of the products of Synthesis examples 1 and 2 were 1.9 and 1.6, respectively, which were substantially in accordance with the initial Mg/Al molar ratio of 2.0.
From the powder X-ray diffraction patterns of FIGS. 2 and 3, X-ray peaks ascribed to LDH were shown, and it was confirmed that the interplanar spacing (d 003) was
Any product has an LDH structure.
From the XPS spectra of FIGS. 5 and 6, it was confirmed that the origin is MnO2The peak of (3) shows that 95% or more of Mn (IV) is present based on the total amount of Mn.
From these results, it was confirmed that: MnO Synthesis without the reduction step of the manganese chloride aqueous solution shown in Synthesis example 1, as in Synthesis example 22Compounding Mg-Al LDH.
Note that MnO in Synthesis example 2 can be considered2The complex Mg-Al LDH was generated as follows.
First, CO is mixed3Pre-roasting the type Mg-Al LDH at 500 ℃ for 2 hours to generate Mg-Al oxide (Mg)1- xAlxO1+x/2) Adding the mixture into a potassium permanganate aqueous solution with the concentration of 0.2 mol/L under nitrogen gas flow, and stirring the mixture for 6 hours at the temperature of 30 ℃, wherein MnO is generated as shown in a formula (3)4Form Mg-Al LDH (Mg)1-xAlx(OH)2(MnO4)x)。
Mg1-xAlxO1+x/2+xMnO4 -+(1+x/2)H2O
→Mg1-xAlx(OH)2(MnO4)x+xOH- (3)
Further, in the aqueous potassium permanganate solution, a reaction represented by the formula (4) occurs to produce MnO2Form Mg-Al LDH (Mg)1- xAlx(OH)2(MnO2)x)。
Mg1-xAlx(OH)2(MnO4)x+x/2H2O
→Mg1-xAlx(OH)2(MnO2)x+3/4xO2+xOH- (4)。
Claims (7)
1. An acidic exhaust gas treatment agent comprising a composite of a Mg-Al-based layered double hydroxide based on at least either one of a manganese oxide and a permanganate compound.
2. An acidic exhaust gas treating agent according to claim 1, wherein the complex compound is at least one of manganese dioxide complex Mg-Al layered double hydroxide and high manganese acid Mg-Al layered double hydroxide.
3. An acidic exhaust gas treating agent according to claim 1 or 2, which comprises a carbonic acid type Mg-Al based layered double hydroxide.
4. A method for treating acidic exhaust gas by using the acidic exhaust gas treating agent according to any one of claims 1 to 3, comprising:
a step (1) of bringing the acidic exhaust gas into contact with the acidic exhaust gas treatment agent and adsorbing acidic substances in the acidic exhaust gas;
a step (2) of desorbing the acidic substance adsorbed to the acidic exhaust gas treatment agent in the step (1) to regenerate the acidic exhaust gas treatment agent; and
and (3) recovering the acidic substance desorbed from the acidic exhaust gas treatment agent in the step (2).
5. The acidic exhaust gas treatment method according to claim 4, wherein a treatment cycle comprising the steps (1) to (3) is repeated, and in the step (1) of at least any one of the treatment cycles 2 nd and thereafter, the acidic exhaust gas treatment agent regenerated in the step (2) of at least any one of the treatment cycles before the treatment cycle is used as at least a part of the acidic exhaust gas treatment agent.
6. An acidic exhaust gas treatment facility for treating an acidic exhaust gas using the acidic exhaust gas treatment agent according to any one of claims 1 to 3, the treatment facility comprising:
a device (1) for bringing the acidic exhaust gas into contact with the acidic exhaust gas treatment agent and adsorbing acidic substances in the acidic exhaust gas;
a device (2) for desorbing the acidic substance adsorbed to the acidic exhaust gas treatment agent in the device (1) to regenerate the acidic exhaust gas treatment agent; and
and a device (3) for recovering the acidic substance desorbed from the acidic exhaust gas treatment agent in the device (2).
7. The acidic exhaust gas treatment method according to claim 4, wherein the manganese dioxide composite Mg-Al layered double hydroxide is produced by a production method that does not require a reduction step, and the manganese dioxide composite Mg-Al layered double hydroxide is produced by adding a Mg-Al oxide to an aqueous potassium permanganate solution, filtering the precipitate, and drying the filtered precipitate.
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| JP2016190199A (en) * | 2015-03-31 | 2016-11-10 | 栗田工業株式会社 | Treatment method for acid exhaust gas generated from combustion facility, combustion facility and acid exhaust gas treatment agent |
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