TW202041464A - Acidic exhaust gas treatment agent, acidic exhaust gas treatment method, and acidic exhaust gas treatment equipment - Google Patents
Acidic exhaust gas treatment agent, acidic exhaust gas treatment method, and acidic exhaust gas treatment equipment Download PDFInfo
- Publication number
- TW202041464A TW202041464A TW109108020A TW109108020A TW202041464A TW 202041464 A TW202041464 A TW 202041464A TW 109108020 A TW109108020 A TW 109108020A TW 109108020 A TW109108020 A TW 109108020A TW 202041464 A TW202041464 A TW 202041464A
- Authority
- TW
- Taiwan
- Prior art keywords
- exhaust gas
- gas treatment
- acidic
- treatment agent
- acid
- Prior art date
Links
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 81
- 229910003023 Mg-Al Inorganic materials 0.000 claims abstract description 75
- 239000000126 substance Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 25
- 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
- 239000002253 acid Substances 0.000 claims description 82
- 239000002131 composite material Substances 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 114
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 49
- 238000002485 combustion reaction Methods 0.000 abstract description 9
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- 239000011777 magnesium Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 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
- 238000012545 processing Methods 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 150000004679 hydroxides Chemical class 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
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 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
- 230000008859 change Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 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
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000006722 reduction reaction Methods 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
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 239000010459 dolomite Substances 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
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 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
- 238000005259 measurement Methods 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
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-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
- 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 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
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 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
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- 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
Description
本發明是有關於一種應用於處理自火力發電站或焚燒設施等燃燒設施產生的酸性排氣的酸性排氣處理劑、酸性排氣處理方法及酸性排氣處理設備。The present invention relates to an acid exhaust gas treatment agent, an acid exhaust gas treatment method and an acid exhaust gas treatment equipment applied to treat acid exhaust gas generated from combustion facilities such as thermal power stations or incineration facilities.
在火力發電或廢棄物焚燒等中產生的燃燒排氣中包含氯化氫或硫氧化物、氮氧化物等有害的酸性物質。因此,針對包含所述酸性物質的酸性排氣,利用用以去除所述酸性物質的各種方法進行處理。The combustion exhaust gas generated during thermal power generation or waste incineration contains harmful acidic substances such as hydrogen chloride, sulfur oxides, and nitrogen oxides. Therefore, the acid exhaust gas containing the acid substance is processed by various methods for removing the acid substance.
針對所述酸性物質中的氯化氫或硫氧化物,利用乾式法或濕式法的處理正在普及,所述乾式法是使用熟石灰等鹼劑進行中和,利用集塵機捕集產物,所述濕式法是利用洗滌器進行中和處理。 另外,針對氮氧化物,利用選擇性觸媒還原法(Selective Catalytic Reduction,SCR)及無觸媒還原法(Selective Non-Catalytic Reduction,SNCR)的處理正在普及,所述選擇性觸媒還原法是將氨或尿素等還原劑混合於燃燒排氣中後,藉由將釩或鉑承載於陶瓷等載體上的觸媒而分解為氮與水,所述無觸媒還原法是向焚燒爐內等直接噴霧氨或尿素等還原劑來分解氮氧化物。Regarding the hydrogen chloride or sulfur oxides in the acidic substance, the dry method or the wet method is becoming popular. The dry method uses an alkali agent such as slaked lime for neutralization, and uses a dust collector to collect the product. The wet method It uses scrubbers for neutralization. In addition, for nitrogen oxides, the use of selective catalytic reduction (Selective Catalytic Reduction, SCR) and non-catalytic reduction (Selective Non-Catalytic Reduction, SNCR) treatment is spreading, the selective catalytic reduction method is After mixing a reducing agent such as ammonia or urea in the combustion exhaust gas, it is decomposed into nitrogen and water by carrying vanadium or platinum on a catalyst such as a ceramic carrier. The catalyst-free reduction method is used in an incinerator, etc. Direct spraying of reducing agents such as ammonia or urea to decompose nitrogen oxides.
然而,所述利用中和處理的處理需要中和產物的處理步驟,另外,需要另行處理氮氧化物。 另外,在利用SCR或SNCR的氮氧化物的處理中,有需要使用還原劑或觸媒等及為此的設備或能量等成本的課題。However, the treatment using the neutralization treatment requires a treatment step of neutralizing the product, and additionally, the nitrogen oxide needs to be treated separately. In addition, in the treatment of nitrogen oxides using SCR or SNCR, there is a problem in that it is necessary to use a reducing agent or a catalyst, and the cost of equipment and energy for this.
針對此種課題,本發明者等人提出了一種可使用碳酸型Mg-Al系層狀雙氫氧化物來有效率且以更低的成本處理所述酸性排氣的方法(參照專利文獻1)。 [現有技術文獻] [專利文獻]In response to such a problem, the inventors of the present invention have proposed a method that can treat the acid exhaust gas efficiently and at a lower cost by using a carbonate-type Mg-Al-based layered double hydroxide (refer to Patent Document 1) . [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2016-190199號公報[Patent Document 1] Japanese Patent Laid-Open No. 2016-190199
[發明所欲解決之課題] 然而,即便利用所述專利文獻1中所記載的處理方法,亦存在一氧化氮的去除處理並不充分的情況。 因此,在使用層狀雙氫氧化物的酸性排氣的處理中,要求提高一氧化氮的去除效率。[The problem to be solved by the invention] However, even if the treatment method described in Patent Document 1 is used, the removal treatment of nitric oxide may be insufficient. Therefore, in the treatment of acidic exhaust gas using layered double hydroxide, it is required to improve the removal efficiency of nitric oxide.
本發明是在此種情況下完成的,目的在於提供一種在使用層狀雙氫氧化物對自火力發電站或焚燒設施等燃燒設施產生的酸性排氣進行處理時,較以往而言可提高一氧化氮的去除效率的酸性排氣處理劑、酸性排氣處理方法及酸性排氣處理設備。The present invention was completed under such circumstances, and its purpose is to provide a method for treating acidic exhaust gas generated from combustion facilities such as thermal power stations or incineration facilities using layered double hydroxides, which can improve by one An acidic exhaust gas treatment agent, an acidic exhaust gas treatment method and an acidic exhaust gas treatment equipment for the removal efficiency of nitrogen oxides.
[解決課題之手段] 本發明基於如下發現:Mg-Al系層狀雙氫氧化物(以下,亦稱為Mg-Al LDH(Layered Double Hydroxide))的由氧化錳等形成的複合化合物的一氧化氮的去除性能優異。[Means to solve the problem] The present invention is based on the discovery that a composite compound formed of manganese oxide or the like of Mg-Al-based layered double hydroxide (hereinafter also referred to as Mg-Al LDH (Layered Double Hydroxide)) has excellent nitric oxide removal performance.
即,本發明提供以下的[1]~[7]。 [1] 一種酸性排氣處理劑,其包含Mg-Al系層狀雙氫氧化物的由氧化錳及過錳酸化合物的至少任一者形成的複合化合物。 [2] 如所述[1]所記載的酸性排氣處理劑,其中所述複合化合物為二氧化錳複合Mg-Al系層狀雙氫氧化物及過錳酸型Mg-Al系層狀雙氫氧化物的至少任一者。 [3] 如所述[1]或[2]所記載的酸性排氣處理劑,其包含碳酸型Mg-Al系層狀雙氫氧化物。That is, the present invention provides the following [1] to [7]. [1] An acidic exhaust gas treatment agent comprising a composite compound formed of at least one of manganese oxide and permanganate compound of Mg-Al-based layered double hydroxide. [2] The acidic exhaust gas treatment agent described in [1], wherein the composite compound is a manganese dioxide composite Mg-Al-based layered double hydroxide and a permanganic acid type Mg-Al-based layered double hydroxide At least any one of hydroxides. [3] The acidic exhaust gas treatment agent as described in [1] or [2], which contains a carbonated Mg—Al-based layered double hydroxide.
[4] 一種酸性排氣處理方法,其是使用如所述[1]至[3]中任一項所記載的酸性排氣處理劑來處理酸性排氣的方法,且包括:使所述酸性排氣與所述酸性排氣處理劑接觸來吸附所述酸性排氣中的酸性物質的步驟(1);使在所述步驟(1)中吸附於所述酸性排氣處理劑的酸性物質脫附而再生所述酸性排氣處理劑的步驟(2);以及回收在所述步驟(2)中自所述酸性排氣處理劑脫附的酸性物質的步驟(3)。 [5] 如所述[4]所記載的酸性排氣處理方法,其中反覆進行包括所述步驟(1)~步驟(3)的處理循環,在所述處理循環的第二次以後的至少任一處理循環的步驟(1)中,將在所述處理循環以前的至少任一處理循環的步驟(2)中再生的酸性排氣處理劑用作所述酸性排氣處理劑的至少一部分。[4] An acid exhaust gas treatment method that uses the acid exhaust gas treatment agent described in any one of [1] to [3] to treat acid exhaust gas, and includes: Step (1) of the exhaust gas being in contact with the acidic exhaust gas treatment agent to adsorb acidic substances in the acidic exhaust gas; and removing the acidic substances adsorbed on the acidic exhaust gas treatment agent in the step (1) Attaching step (2) of regenerating the acidic exhaust gas treatment agent; and step (3) of recovering the acidic substances desorbed from the acidic exhaust gas treatment agent in the step (2). [5] The acid exhaust gas treatment method described in [4], wherein the treatment cycle including the steps (1) to (3) is repeatedly performed, and at least any time after the second time of the treatment cycle is repeated. In step (1) of one treatment cycle, the acidic exhaust gas treatment agent regenerated in step (2) of at least any treatment cycle before the treatment cycle is used as at least a part of the acidic exhaust gas treatment agent.
[6] 一種酸性排氣處理設備,其是使用如所述[1]至[3]中任一項所記載的酸性排氣處理劑來處理酸性排氣的設備,且包括:使所述酸性排氣與所述酸性排氣處理劑接觸來吸附所述酸性排氣中的酸性物質的單元(1);使在所述單元(1)中吸附於所述酸性排氣處理劑的酸性物質脫附而再生所述酸性排氣處理劑的單元(2);以及回收在所述單元(2)中自所述酸性排氣處理劑脫附的酸性物質的單元(3)。 [7] 如所述[4]所記載的酸性排氣處理方法,其中所述二氧化錳複合Mg-Al系層狀雙氫氧化物是由向過錳酸鉀水溶液中添加Mg-Al氧化物,對沈澱物進行過濾,並加以乾燥而生成的無需還原步驟的製法所得。[6] An acid exhaust gas treatment facility that uses the acid exhaust gas treatment agent described in any one of [1] to [3] to treat acid exhaust gas, and includes: Unit (1) for the exhaust gas to contact the acidic exhaust gas treatment agent to adsorb the acidic substances in the acidic exhaust gas; to remove the acidic substances adsorbed on the acidic exhaust gas treatment agent in the unit (1) Attached is a unit (2) that regenerates the acidic exhaust gas treatment agent; and a unit (3) that recovers acidic substances desorbed from the acidic exhaust gas treatment agent in the unit (2). [7] The acid exhaust gas treatment method described in [4], wherein the manganese dioxide composite Mg-Al layered double hydroxide is made by adding Mg-Al oxide to an aqueous potassium permanganate solution , The precipitate is filtered and dried to produce a method that does not require a reduction step.
[發明的效果] 藉由使用本發明的酸性排氣處理劑,可對自火力發電站或焚燒設施等燃燒設施產生的氯化氫、硫氧化物及氮氧化物等酸性排氣同時進行去除處理,特別是,一氧化氮的去除效率較使用以往的層狀雙氫氧化物的情況而言提高。 另外,根據使用所述酸性排氣處理劑的本發明的酸性排氣處理方法,較以往而言可以少的處理劑量有效率地去除酸性排氣,另外,可再生利用所述酸性排氣處理劑。 另外,根據本發明的酸性排氣處理裝置,可適宜地進行所述酸性排氣處理方法,較以往而言可有效率且以低成本處理酸性排氣。[Effects of the invention] By using the acidic exhaust gas treatment agent of the present invention, it is possible to simultaneously remove acidic exhaust gas such as hydrogen chloride, sulfur oxides, and nitrogen oxides generated from combustion facilities such as thermal power stations or incineration facilities, especially nitrogen monoxide. The removal efficiency is higher than that of the conventional layered double hydroxide. In addition, according to the acid exhaust gas treatment method of the present invention using the acid exhaust gas treatment agent, acid exhaust gas can be efficiently removed with a smaller treatment amount than in the past, and the acid exhaust gas treatment agent can be recycled . In addition, according to the acid exhaust gas treatment device of the present invention, the acid exhaust gas treatment method can be suitably performed, and acid exhaust gas can be treated more efficiently and at low cost than in the past.
以下,對本發明的酸性排氣處理劑、及使用其的酸性排氣處理方法以及酸性排氣處理設備進行詳細說明。Hereinafter, the acid exhaust gas treatment agent of the present invention, the acid exhaust gas treatment method and the acid exhaust gas treatment equipment using the same will be described in detail.
[酸性排氣處理劑] 本發明的酸性排氣處理劑包含Mg-Al LDH的由氧化錳及過錳酸化合物的至少任一者(以下,亦稱為Mn-O化合物)形成的複合化合物。 如上所述,藉由使用將Mg-Al LDH製成由錳與氧的化合物(Mn-O化合物)形成的複合化合物所得者作為酸性排氣處理劑,與使用以往的層狀雙氫氧化物即Mg-Al LDH等的情況相比,可提高一氧化氮的去除效率。 推測其原因在於:Mg-Al LDH自身雖難以吸附一氧化氮,但藉由經複合化的Mn-O化合物的觸媒作用,一氧化氮被氧化成二氧化氮,進而容易被氧化成硝酸根離子,從而容易吸附於Mg-Al LDH的複合化合物。[Acid exhaust treatment agent] The acidic exhaust gas treatment agent of the present invention contains a composite compound of Mg-Al LDH composed of at least one of manganese oxide and permanganate compound (hereinafter, also referred to as Mn-O compound). As mentioned above, by using Mg-Al LDH as a composite compound of manganese and oxygen compound (Mn-O compound) as an acidic exhaust gas treatment agent, it is different from the conventional layered double hydroxide. Compared with the case of Mg-Al LDH, it can improve the removal efficiency of nitric oxide. It is presumed that the reason is that although Mg-Al LDH itself is difficult to adsorb nitric oxide, it is oxidized to nitrogen dioxide by the catalytic action of the composite Mn-O compound, and then easily oxidized to nitrate. Ions, which are easily adsorbed to the Mg-Al LDH complex compound.
錳可取+2~+7的氧化數,就作為氧化觸媒的作用的觀點而言,較佳為氧化數大者。作為所述複合化合物,就合成容易性等觀點而言,例如較佳為由氧化數+4的錳形成的二氧化錳複合Mg-Al層狀雙氫氧化物(以下,亦稱為MnO2 複合Mg-Al LDH)或由氧化數+7的錳形成的過錳酸型Mg-Al系層狀雙氫氧化物(以下,亦稱為MnO4 型Mg-Al LDH)等。所述複合化合物可為單獨一種,亦可包含兩種以上。Manganese may have an oxidation number of +2 to +7, and from the viewpoint of its function as an oxidation catalyst, it is preferably one with a larger oxidation number. As the composite compound, from the viewpoint of ease of synthesis and the like, for example, a manganese dioxide composite Mg-Al layered double hydroxide (hereinafter, also referred to as MnO 2 composite) formed of manganese with oxidation number +4 Mg-Al LDH) or permanganic acid type Mg-Al layered double hydroxide formed of manganese with oxidation number +7 (hereinafter, also referred to as MnO 4 type Mg-Al LDH). The composite compound may be one kind alone or two or more kinds.
MnO2 複合Mg-Al LDH的結構式是由下述式(1)表示,另外,MnO4 型Mg-Al LDH的結構式是由下述式(2)表示。 Mg1-xAlx( OH)2 (MnO2 )2.5x (Cl)x ·mH2 O (1) Mg1-xAlx( OH)2 (MnO4 )x ·mH2 O (2) 在所述式(1)及式(2)中,通常為x=0.20~0.40、m=1~12。The structural formula of the MnO 2 composite Mg-Al LDH is represented by the following formula (1), and the structural formula of the MnO 4 type Mg-Al LDH is represented by the following formula (2). Mg 1-xAlx( OH) 2 (MnO 2 ) 2.5x (Cl) x ·mH 2 O (1) Mg 1-xAlx( OH) 2 (MnO 4 ) x ·mH 2 O (2) In the formula ( 1) and formula (2), usually x=0.20~0.40, m=1~12.
在所述酸性排氣處理劑中較佳為包含碳酸型Mg-Al系層狀雙氫氧化物(以下,亦稱為CO3 型Mg-Al LDH)。 如所述專利文獻1所記載般,CO3 型Mg-Al LDH為可適宜地用於處理酸性排氣的化合物,可有效率地去除酸性排氣中所含的例如氯化氫、二氧化硫、二氧化氮等一氧化氮以外的酸性化合物。因此,較佳為與所述複合化合物併用。 所述情況下,所述酸性排氣處理劑中的所述複合化合物與CO3 型Mg-Al LDH的含量的比例並無特別限定,可根據要處理的酸性排氣中所含的一氧化氮的量等酸性排氣的成分組成來適宜設定。The acidic exhaust gas treatment agent preferably contains carbonic acid type Mg—Al layered double hydroxide (hereinafter, also referred to as CO 3 type Mg—Al LDH). As described in Patent Document 1, the CO 3 type Mg-Al LDH is a compound that can be suitably used to treat acid exhaust gas, and can efficiently remove, for example, hydrogen chloride, sulfur dioxide, and nitrogen dioxide contained in acid exhaust gas. Acidic compounds other than nitric oxide. Therefore, it is preferably used in combination with the composite compound. In this case, the ratio of the content of the composite compound in the acid exhaust gas treatment agent to the content of CO 3 type Mg-Al LDH is not particularly limited, and may be based on the nitrogen monoxide contained in the acid exhaust gas to be treated. The amount of acid exhaust gas and the composition of the acid exhaust are appropriately set.
CO3 型Mg-Al LDH作為水滑石,亦存在天然產出的黏土礦物,但在進行合成的情況下,其合成方法並無特別限定,可使用公知的方法(例如,所述專利文獻1中所記載的方法)。 例如,可藉由如下方式來獲得:將硝酸鎂(Mg(NO3 )2 )與硝酸鋁(Al(NO3 )3 )以Mg/Al=2/1(莫耳比)混合而成的水溶液保持為pH值10.5,同時滴加至碳酸鈉(Na2 CO3 )水溶液中。具體而言,可利用下述實施例中所示的方法來合成。CO 3 type Mg-Al LDH as hydrotalcite, there are naturally occurring clay minerals, but in the case of synthesis, the synthesis method is not particularly limited, and a known method can be used (for example, in the patent document 1 Documented method). For example, it can be obtained as follows: an aqueous solution of magnesium nitrate (Mg(NO 3 ) 2 ) and aluminum nitrate (Al(NO 3 ) 3 ) mixed with Mg/Al=2/1 (molar ratio) Keep the pH at 10.5, while adding dropwise to the sodium carbonate (Na 2 CO 3 ) aqueous solution. Specifically, it can be synthesized by the method shown in the following examples.
另外,MnO2 複合Mg-Al LDH及MnO4 型Mg-Al LDH的合成方法亦並無特別限定,可將CO3 型Mg-Al LDH作為原料化合物,利用由其插層帶來的陰離子交換功能而進行合成。 例如,對CO3 型Mg-Al LDH在500℃下進行煆燒而獲得Mg-Al氧化物後,添加混合於過錳酸鉀(KMnO4 )水溶液中,藉此可合成取入有過錳酸根離子(MnO4 - )的MnO4 型Mg-Al LDH。 進而,MnO4 型Mg-Al LDH在過錳酸鉀(KMnO4 )水溶液中變化成MnO2 複合Mg-Al LDH。 另外,所述MnO4 型Mg-Al LDH可藉由添加混合於氯化錳(MnCl2 )水溶液中來合成MnO2 複合Mg-Al LDH。In addition, the synthesis method of MnO 2 composite Mg-Al LDH and MnO 4 type Mg-Al LDH is not particularly limited. CO 3 type Mg-Al LDH can be used as a raw material compound to utilize the anion exchange function brought by its intercalation And synthesize. For example, after sintering CO 3 type Mg-Al LDH at 500°C to obtain Mg-Al oxide, it is added and mixed with potassium permanganate (KMnO 4 ) aqueous solution, thereby synthesizing and taking in permanganate ion (MnO 4 -) MnO 4 type Mg-Al LDH. Furthermore, MnO 4 type Mg-Al LDH is changed into MnO 2 composite Mg-Al LDH in a potassium permanganate (KMnO 4 ) aqueous solution. In addition, the MnO 4 type Mg-Al LDH can be added and mixed in a manganese chloride (MnCl 2 ) aqueous solution to synthesize MnO 2 composite Mg-Al LDH.
所述酸性排氣處理劑亦可在不妨礙本發明的效果的範圍內包含例如氫氧化鈣(熟石灰)、氧化鈣、碳酸氫鈉(Sodium bicarbonate)、碳酸鈉、氫氧化白雲石、輕燒白雲石、氫氧化鋁、氧化鋁、氫氧化鎂、氧化鎂等層狀雙氫氧化物以外的藥劑。其中,於在後述的酸性排氣處理方法中,再生所述酸性排氣處理劑並將其供於再利用的情況下,就再生品的純度或回收操作等觀點而言,較佳為不含該些藥劑。The acidic exhaust gas treatment agent may include, for example, calcium hydroxide (slaked lime), calcium oxide, sodium bicarbonate, sodium carbonate, hydroxide dolomite, and light burned dolomite within a range that does not hinder the effects of the present invention. Agents other than layered double hydroxides such as stone, aluminum hydroxide, aluminum oxide, magnesium hydroxide, and magnesium oxide. Among them, in the acid exhaust gas treatment method described later, in the case of regenerating the acid exhaust gas treatment agent and supplying it for reuse, it is preferable to not contain any from the viewpoint of the purity of the regenerated product or the recovery operation. These medicines.
[酸性排氣處理方法] 使用所述酸性排氣處理劑來處理酸性排氣的方法並無特別限定,所述酸性排氣處理劑(以下,亦簡稱為處理劑)較佳為應用於本發明的酸性排氣處理方法中。 本發明的酸性排氣處理方法為包括如下步驟的處理方法:使酸性排氣與所述處理劑接觸來吸附所述酸性排氣中的酸性物質的步驟(1);使在所述步驟(1)中吸附於所述處理劑的酸性物質脫附而再生所述處理劑的步驟(2);以及回收在所述步驟(2)中自所述處理劑脫附的酸性物質的步驟(3)。 根據如上所述的處理方法,可再利用所再生的處理劑。另外,酸性物質例如溶解於水中而以酸(水溶液)的形式回收,所述酸亦可供於工業用途等中的利用。[Acid exhaust gas treatment method] The method of using the acid exhaust gas treatment agent to treat acid exhaust gas is not particularly limited. The acid exhaust gas treatment agent (hereinafter, also referred to as the treatment agent for short) is preferably applied to the acid exhaust gas treatment method of the present invention . The acid exhaust gas treatment method of the present invention is a treatment method including the steps of: contacting acid exhaust gas with the treatment agent to adsorb acidic substances in the acid exhaust gas (1); Step (2) of desorbing the acidic substance adsorbed on the treatment agent to regenerate the treatment agent in ); and step (3) of recovering the acidic substance desorbed from the treatment agent in the step (2) . According to the treatment method described above, the regenerated treatment agent can be reused. In addition, the acidic substance is, for example, dissolved in water and recovered in the form of an acid (aqueous solution), and the acid can also be utilized in industrial applications and the like.
在所述步驟(1)中,藉由所述處理劑中的所述複合化合物,一氧化氮被氧化,另外,藉由在層狀雙氫氧化物的層間取入酸性排氣中的酸性物質的陰離子交換等,所述酸性物質吸附於所述處理劑。In the step (1), nitric oxide is oxidized by the complex compound in the treatment agent, and the acidic substance in the acid exhaust is taken in between the layers of the layered double hydroxide. Anion exchange, etc., the acidic substance is adsorbed on the treatment agent.
繼而,在所述步驟(2)中,藉由可逆的陰離子交換等而使吸附於所述處理劑的所述酸性物質自所述處理劑脫附。此時的陰離子交換例如可與CO3 型Mg-Al LDH、MnO2 複合Mg-Al LDH及MnO4 型Mg-Al LDH的合成方法同樣地藉由使用各種水溶液並加以混合攪拌來進行,由此可容易地再生處理劑。 以所述方式再生的處理劑可進行再利用,因此可減低酸性排氣的處理成本。Then, 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 at this time can be performed, for example, by using various aqueous solutions and mixing and stirring them in the same way as the synthesis method of CO 3 type Mg-Al LDH, MnO 2 composite Mg-Al LDH and MnO 4 type Mg-Al LDH. The treatment agent can be easily regenerated. The treatment agent regenerated in this way can be reused, so the treatment cost of acid exhaust gas can be reduced.
在所述步驟(3)中,回收在所述步驟(2)中自所述處理劑脫附的酸性物質。例如,可溶解於水中而以酸(水溶液)的形式回收,所述酸亦可供於工業用途等中的利用。 如上所述,本發明的處理方法不僅對於所述處理劑而言,而且對於作為處理對象的酸性排氣而言,亦是再循環性優異的方法。In the step (3), the acidic substance desorbed from the treatment agent in the step (2) is recovered. For example, it can be dissolved in water and recovered in the form of an acid (aqueous solution), and the acid can also be used in industrial applications. As described above, the treatment method of the present invention is not only for the treatment agent, but also for the acid exhaust gas that is the treatment target, and is also a method having excellent recirculation properties.
在所述處理方法中,較佳為反覆進行包括所述步驟(1)~步驟(3)的處理循環,在所述處理循環的第二次以後的至少任一處理循環的步驟(1)中,將在所述處理循環以前的至少任一處理循環的步驟(2)中再生的處理劑用作所述處理劑的至少一部分。 如上所述,在反覆進行所述處理方法的情況下,藉由再利用在前一步驟中再生的處理劑,可減低酸性排氣的處理所需的處理劑的總使用量,亦會減低酸性排氣的處理成本。In the treatment method, it is preferable to repeatedly perform the treatment cycle including the steps (1) to (3), and in step (1) of at least any treatment cycle after the second time of the treatment cycle , The treatment agent regenerated in step (2) of at least any treatment cycle before the treatment cycle is used as at least a part of the treatment agent. As described above, when the treatment method is repeatedly performed, by reusing the treatment agent regenerated in the previous step, the total usage of the treatment agent required for the treatment of acid exhaust gas can be reduced, and the acidity will also be reduced. The cost of exhaust gas treatment.
如上所述的本發明的酸性排氣的處理方法可利用一種處理劑對酸性排氣中的各種酸性物質同時進行去除處理,因此作業效率優異。特別是,藉由使用所述複合化合物作為處理劑,較以往而言可提高一氧化氮的去除效率。 另外,在處理時不會產生中和產物而可減輕伴隨處理所產生的廢棄物的處理負荷。As described above, the acid exhaust gas treatment method of the present invention can simultaneously remove various acidic substances in the acid exhaust gas using one treatment agent, and therefore has excellent work efficiency. In particular, by using the composite compound as a treatment agent, the removal efficiency of nitric oxide can be improved compared to the past. In addition, no neutralized product is generated during processing, and the processing load of waste generated with processing can be reduced.
[酸性排氣處理設備] 用以使用所述酸性排氣處理劑來處理酸性排氣的設備並無特別限定,所述處理劑較佳為應用於本發明的酸性排氣處理設備中。 本發明的酸性排氣處理設備為包括如下單元的處理設備:使酸性排氣與所述處理劑接觸來吸附所述酸性排氣中的酸性物質的單元(1);使在所述單元(1)中吸附於所述處理劑的酸性物質脫附而再生所述處理劑的單元(2);以及回收在所述單元(2)中自所述處理劑脫附的酸性物質的單元(3)。[Sour exhaust gas treatment equipment] The equipment for treating acid exhaust gas using the acid exhaust gas treatment agent is not particularly limited, and the treatment agent is preferably applied to the acid exhaust gas treatment equipment of the present invention. The acid exhaust gas treatment equipment of the present invention is a treatment equipment including a unit (1) that makes acid exhaust gas contact with the treatment agent to adsorb acidic substances in the acid exhaust gas; Unit (2) for desorbing the acidic substance adsorbed on the treatment agent to regenerate the treatment agent; and unit (3) for recovering the acidic substance desorbed from the treatment agent in the unit (2) .
所述單元(1)例如可藉由在收容有所述處理劑的容器中設置酸性排氣的流通路而構成。 所述單元(2)例如可構成為如下浸漬槽:針對自流通酸性排氣後的所述容器內取出的處理劑,藉由與所述CO3 型Mg-Al LDH、MnO2 複合Mg-Al LDH及MnO4 型Mg-Al LDH的合成方法相同的方法,根據使其複合化為Mg-Al LDH的化學種而浸漬於各種水溶液中,並進行混合攪拌。 所述單元(3)例如可構成為溶解於水中而以酸(水溶液)的形式回收的水溶液收容罐。The unit (1) can be configured by, for example, providing a flow path of acid exhaust gas in a container containing the processing agent. The unit (2) may be configured as, for example, a dipping tank: for the treatment agent taken out of the container after self-circulating acid exhaust gas, by combining Mg-Al with the CO 3 type Mg-Al LDH, MnO 2 The synthesis method of LDH and MnO 4 type Mg-Al LDH is the same, according to the chemical species that is compounded into Mg-Al LDH, immersed in various aqueous solutions and mixed and stirred. The unit (3) may be configured as an aqueous solution storage tank that is dissolved in water and recovered as an acid (aqueous solution), for example.
所述酸性排氣處理設備可附設於火力發電或廢棄物焚燒等的燃燒設備中。例如,在處理廢棄物焚燒爐中產生的酸性排氣的情況下,可構成為:繼焚燒爐主體的燃燒排氣系統中依次設置的鍋爐、排氣冷卻裝置、集塵機之後,設置所述酸性排氣處理設備,並利用誘導通風機等將來自所述酸性排氣處理設備的處理完畢的排氣導入煙筒而自所述煙筒放出至大氣中。 [實施例]The acid exhaust gas treatment equipment may be attached to combustion equipment such as thermal power generation or waste incineration. For example, in the case of processing acid exhaust gas generated in a waste incinerator, it can be configured to install the acid exhaust gas after the boiler, exhaust gas cooling device, and dust collector are installed in the combustion exhaust system of the incinerator body. The exhaust gas processing equipment is used to introduce the processed exhaust gas from the acid exhaust gas processing equipment into the chimney using an induction ventilator or the like, and the exhaust gas is released from the chimney into the atmosphere. [Example]
以下,對本發明進一步詳細說明,但本發明並不由下述實施例限定。Hereinafter, the present invention will be described in further detail, but the present invention is not limited by the following examples.
[合成例1] MnO2 複合Mg-Al LDH的合成 使用硝酸鎂六水合物及硝酸鋁九水合物來製備鎂濃度0.33莫耳/L、鋁濃度0.17莫耳/L的混合水溶液(鎂/鋁=2/1(莫耳比))。 在30℃下,一邊對所述混合溶液進行攪拌一邊滴加至濃度0.1莫耳/L的碳酸鈉水溶液中。此時,藉由滴加濃度1.25莫耳/L的氫氧化鈉水溶液而將pH值保持為10.5。 滴加結束後,在30℃下攪拌1小時。其後,對沈澱物進行過濾,反復清洗後,在40℃下減壓乾燥40小時而獲得CO3 型Mg-Al LDH。 將所獲得的CO3 型Mg-Al LDH在500℃下煆燒2小時後,在氮氣氣流下投入至濃度0.2莫耳/L的過錳酸鉀水溶液中,在30℃下攪拌6小時。其後,對沈澱物進行過濾,反復清洗後,將在40℃下減壓乾燥40小時而獲得的產物在氮氣氣流下投入至濃度0.1莫耳/L的氯化錳水溶液中,在30℃下攪拌3小時。其後,對沈澱物進行過濾,反復清洗後,在40℃下減壓乾燥,從而獲得MnO2 複合Mg-Al LDH(Mg0.62 Al0.38 (OH)2 (MnO2 )0.95 (Cl)0.38 ·1.13H2 O)。[Synthesis example 1] The synthesis of MnO 2 composite Mg-Al LDH uses magnesium nitrate hexahydrate and aluminum nitrate nonahydrate to prepare a mixed aqueous solution (magnesium/aluminum) with a magnesium concentration of 0.33 mol/L and an aluminum concentration of 0.17 mol/L = 2/1 (mole ratio)). At 30°C, the mixed solution was added dropwise to a sodium carbonate aqueous solution with a concentration of 0.1 mol/L while stirring the mixed solution. At this time, the pH value was maintained at 10.5 by dropping a sodium hydroxide aqueous solution with a concentration of 1.25 mol/L. After the dropwise addition, it was stirred at 30°C for 1 hour. After that, the precipitate was filtered, washed repeatedly, and dried under reduced pressure at 40°C for 40 hours to obtain CO 3 type Mg-Al LDH. After the obtained CO 3 type Mg-Al LDH was sintered at 500°C for 2 hours, it was poured into a 0.2 mol/L potassium permanganate aqueous solution under a nitrogen stream, and stirred at 30°C for 6 hours. After that, the precipitate was filtered, and after repeated washing, the product obtained by drying under reduced pressure at 40°C for 40 hours was poured into an aqueous solution of manganese chloride with a concentration of 0.1 mol/L under a nitrogen gas stream at 30°C Stir for 3 hours. After that, the precipitate was filtered, washed repeatedly, and dried under reduced pressure at 40°C to obtain MnO 2 composite Mg-Al LDH (Mg 0.62 Al 0.38 (OH) 2 (MnO 2 ) 0.95 (Cl) 0.38 ·1.13 H 2 O).
[合成例2] MnO2 複合Mg-Al LDH的合成 使用硝酸鎂六水合物及硝酸鋁九水合物來製備鎂濃度0.33莫耳/L、鋁濃度0.17莫耳/L的混合水溶液(鎂/鋁=2/1(莫耳比))。 在30℃下,一邊對所述混合溶液進行攪拌一邊滴加至濃度0.1莫耳/L的碳酸鈉水溶液中。此時,藉由滴加濃度1.25莫耳/L的氫氧化鈉水溶液而將pH值保持為10.5。 滴加結束後,在30℃下攪拌1小時。其後,對沈澱物進行過濾,反復清洗後,在40℃下減壓乾燥40小時而獲得CO3 型Mg-Al LDH。 將所獲得的CO3 型Mg-Al LDH在500℃下煆燒2小時後,在氮氣氣流下投入至濃度0.2莫耳/L的過錳酸鉀水溶液中,在30℃下攪拌6小時。其後,對沈澱物進行過濾,反復清洗後,在40℃下減壓乾燥40小時。[Synthesis example 2] Synthesis of MnO 2 composite Mg-Al LDH Magnesium nitrate hexahydrate and aluminum nitrate nonahydrate were used to prepare a mixed aqueous solution (magnesium/aluminum) with a magnesium concentration of 0.33 mol/L and an aluminum concentration of 0.17 mol/L = 2/1 (mole ratio)). At 30°C, the mixed solution was added dropwise to a sodium carbonate aqueous solution with a concentration of 0.1 mol/L while stirring the mixed solution. At this time, the pH value was maintained at 10.5 by dropping a sodium hydroxide aqueous solution with a concentration of 1.25 mol/L. After the dropwise addition, it was stirred at 30°C for 1 hour. After that, the precipitate was filtered, washed repeatedly, and dried under reduced pressure at 40°C for 40 hours to obtain CO 3 type Mg-Al LDH. After the obtained CO 3 type Mg-Al LDH was sintered at 500°C for 2 hours, it was poured into a 0.2 mol/L potassium permanganate aqueous solution under a nitrogen stream, and stirred at 30°C for 6 hours. Thereafter, the precipitate was filtered, washed repeatedly, and dried under reduced pressure at 40°C for 40 hours.
再者,合成例1及合成例2中的CO3 型Mg-Al LDH、MnO4 型Mg-Al LDH及MnO2 複合Mg-Al LDH藉由粉末X射線繞射測定法(粉末XRD)來進行相鑒定。關於CO3 型Mg-Al LDH,將粉末X射線繞射圖示於圖4中。再者,所使用的X射線繞射測定裝置為理學股份有限公司製造的「RINT-2200VHF」,使用CuKα射線(1.5418A)作為特性X射線進行測定。另外,關於由Mn-O化合物形成的複合化合物,亦示出由感應耦合電漿發光分光分析法(Inductively Coupled Plasma-Atomic Emission Spectrometry,ICP-AES)所得的元素分析值。另外,合成例1及合成例2中的MnO4 型Mg-Al LDH及MnO2 複合Mg-Al LDH是藉由使用X射線光電子分光法(XPS)來特定Mn的氧化數而鑒定。Furthermore, the CO 3 type Mg-Al LDH, MnO 4 type Mg-Al LDH, and MnO 2 composite Mg-Al LDH in Synthesis Example 1 and Synthesis Example 2 were measured by powder X-ray diffraction measurement (powder XRD) Phase identification. Regarding the CO 3 type Mg-Al LDH, the powder X-ray diffraction diagram is shown in FIG. 4. In addition, the X-ray diffraction measurement device used was "RINT-2200VHF" manufactured by Rigaku Co., Ltd., and CuKα rays (1.5418A) were used as characteristic X-rays for measurement. In addition, regarding the composite compound formed of the Mn-O compound, the elemental analysis value obtained by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) is also shown. In addition, the MnO 4 type Mg-Al LDH and the MnO 2 composite Mg-Al LDH in Synthesis Example 1 and Synthesis Example 2 were identified by specifying the oxidation number of Mn using X-ray photoelectron spectroscopy (XPS).
[酸性排氣處理性能評價試驗] (實施例1) 將1.0 g的合成例1中所獲得的MnO2 複合Mg-Al LDH填充於管狀電爐的反應管(內徑16 mm)內的玻璃棉上。將管狀電爐的設定溫度設為170℃,利用質量流量控制器對試驗氣體(載氣:氮氣、一氧化氮氣體濃度150 volppm、氧氣濃度10 vol%)進行流量調整,以線速度1.0 m/min流入反應管中。藉由利用定電位電解法的燃燒排氣分析計(泰斯特(TEST)股份有限公司製造)來測定反應管的出口氣體的NOx 濃度的經時變化(90分鐘)。[Acid exhaust gas treatment performance evaluation test] (Example 1) 1.0 g of the MnO 2 composite Mg-Al LDH obtained in Synthesis Example 1 was filled on the glass wool in the reaction tube (inner diameter 16 mm) of the tubular electric furnace . Set the set temperature of the tubular electric furnace to 170℃, use the mass flow controller to adjust the flow rate of the test gas (carrier gas: nitrogen, nitric oxide gas concentration 150 volppm, oxygen concentration 10 vol%) at a linear velocity of 1.0 m/min Flow into the reaction tube. By using a constant potential electrolysis of the combustion exhaust gas analyzer (Taisite (TEST) Co., Ltd.) to determine the change over time of the NO x concentration in the outlet gas of the reaction tube (90 minutes).
(比較例1) 在實施例1中,將MnO2 複合Mg-Al LDH變更為合成例1的合成過程中所獲得的CO3 型Mg-Al LDH,除此以外,與實施例1同樣地進行評價試驗。(Comparative Example 1) In Example 1, the MnO 2 composite Mg-Al LDH was changed to the CO 3 type Mg-Al LDH obtained in the synthesis process of Synthesis Example 1, except that it was performed in the same manner as Example 1 Evaluation test.
將實施例1及比較例1中的反應管的出口氣體的NOx 濃度的經時變化製成圖表而示於圖1中。 另外,根據NOx 濃度的累計濃度來求出試驗氣體中的一氧化氮氣體的反應率,結果實施例1為91.5 vol%,比較例1為2.2 vol%。 根據該些結果而確認到,二氧化錳與Mg-Al系層狀雙氫氧化物的複合化合物較CO3 型Mg-Al LDH而言一氧化氮的去除性能優異。The change chart when the NO x concentration in the outlet gas of the reaction tube in Example 1 and Comparative Example 1 by 1 and shown in FIG. In addition, the reaction rate of the nitric oxide gas in the test gas was calculated from the cumulative concentration of the NO x concentration. As a result, Example 1 was 91.5 vol%, and Comparative Example 1 was 2.2 vol%. From these results, it was confirmed that the composite compound of manganese dioxide and Mg-Al-based layered double hydroxide is superior to CO 3 type Mg-Al LDH in removing nitric oxide.
[由合成例1及合成例2所得的MnO2 複合Mg-Al LDH的存在比的分析] 將由合成例1及合成例2所得的產物的粉末X射線繞射圖示於圖2及圖3中。另外,將由合成例1及合成例2所得的產物的XPS光譜示於圖5及圖6中。 根據元素分析值,合成例1及合成例2的產物的Mg/Al莫耳比分別為1.9及1.6,與初始Mg/Al莫耳比2.0大致一致。 根據圖2及圖3的粉末X射線繞射圖,均示出歸屬於LDH的X射線峰值,面間隔(d003 )亦為7.6 Å、7.5 Å,任一產物均確認到LDH構造。 根據圖5及圖6的XPS光譜,確認到源自MnO2 的Mn(IV)的峰值,根據峰值面積,均確認到相對於Mn的總量,存在95%以上的Mn(IV)。 根據該些結果而確認到:即便如合成例2般無合成例1所示的投入至氯化錳水溶液中的還原步驟,亦可合成MnO2 複合Mg-Al LDH。[Analysis of the abundance ratio of MnO 2 composite Mg-Al LDH obtained in Synthesis Example 1 and Synthesis Example 2] The powder X-ray diffraction diagrams of the products obtained in Synthesis Example 1 and Synthesis Example 2 are shown in FIGS. 2 and 3 . In addition, the XPS spectra of the products obtained in Synthesis Example 1 and Synthesis Example 2 are shown in FIGS. 5 and 6. According to the elemental analysis values, the Mg/Al molar ratios of the products of Synthesis Example 1 and Synthesis Example 2 are 1.9 and 1.6, respectively, which are roughly consistent with the initial Mg/Al molar ratio of 2.0. According to the powder X-ray diffraction diagrams of Figures 2 and 3, both show the X-ray peaks attributed to LDH, and the interplanar spacing (d 003 ) is also 7.6 Å and 7.5 Å, and the LDH structure is confirmed for either product. From the XPS spectra of FIGS. 5 and 6, the peak of Mn(IV) derived from MnO 2 was confirmed, and from the peak area, it was confirmed that 95% or more of Mn(IV) was present relative to the total amount of Mn. From these results, it was confirmed that even if there is no reduction step in the manganese chloride aqueous solution shown in Synthesis Example 1, as in Synthesis Example 2, MnO 2 composite Mg-Al LDH can be synthesized.
再者,認為在合成例2中,MnO2 複合Mg-Al LDH是以如下方式生成。 首先,將CO3 型Mg-Al LDH在500℃煆燒2小時後,將所生成的Mg-Al氧化物(Mg1-x Alx O1+x/2 )在氮氣氣流下投入至濃度0.2莫耳/L的過錳酸鉀水溶液中,在30℃下攪拌6小時後,如式(3)所示,生成MnO4 型Mg-Al LDH(Mg1-x Alx (OH)2 (MnO4 )x )。 Mg1-x Alx O1+x/2 +xMnO4 - +(1+x/2)H2 O →Mg1-x Alx (OH)2 (MnO4 )x +xOH- (3) 進而,在過錳酸鉀水溶液中,產生式(4)所示的反應,從而生成MnO2 型Mg-Al LDH(Mg1-x Alx (OH)2 (MnO2 )x )。 Mg1-xAlx( OH)2 (MnO4 )x +x/2H2 O →Mg1-x Alx (OH)2 (MnO2 )x +3/4xO2 +xOH- (4)Furthermore, it is considered that in Synthesis Example 2, the MnO 2 composite Mg-Al LDH is produced as follows. First, the CO 3 type Mg-Al LDH is sintered at 500°C for 2 hours, and then the generated Mg-Al oxide (Mg 1-x Al x O 1+x/2 ) is charged to a concentration of 0.2 under nitrogen flow Mole/L potassium permanganate aqueous solution, after stirring at 30℃ for 6 hours, as shown in formula (3), MnO 4 type Mg-Al LDH (Mg 1-x Al x (OH) 2 (MnO 4 ) x ). Mg 1-x Al x O 1 + x / 2 + xMnO 4 - + (1 + x / 2) H 2 O → Mg 1-x Al x (OH) 2 (MnO 4) x + xOH - (3) Further , In the potassium permanganate aqueous solution, the reaction shown in formula (4) occurs, thereby generating MnO 2 type Mg-Al LDH (Mg 1-x Al x (OH) 2 (MnO 2 ) x ). Mg 1-xAlx (OH) 2 (MnO 4) x + x / 2H 2 O → Mg 1-x Al x (OH) 2 (MnO 2) x + 3 / 4xO 2 + xOH - (4)
無no
圖1是表示實施例的酸性排氣處理性能評價試驗中的反應管出口氣體的NOx 濃度的經時變化的圖表。 圖2是合成例1的產物的粉末X射線繞射圖。 圖3是合成例2的產物的粉末X射線繞射圖。 圖4是CO3 型Mg-Al LDH的粉末X射線繞射圖。 圖5是合成例1的產物的X射線光電子分光法(X-ray photoelectric spectrophotometry,XPS)光譜。 圖6是合成例2的產物的XPS光譜。FIG. 1 is a graph showing change over time of the NO x concentration of the acidic gas outlet of the reaction tube an exhaust gas treatment performance evaluation tests by the embodiment. 2 is a powder X-ray diffraction diagram of the product of Synthesis Example 1. FIG. 3 is a powder X-ray diffraction diagram of the product of Synthesis Example 2. FIG. Fig. 4 is a powder X-ray diffraction diagram of CO 3 type Mg-Al LDH. FIG. 5 is an X-ray photoelectric spectrophotometry (XPS) spectrum of the product of Synthesis Example 1. FIG. Fig. 6 is an XPS spectrum of the product of Synthesis Example 2.
Claims (7)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019-080221 | 2019-04-19 | ||
JP2019080221 | 2019-04-19 | ||
JP2019193749A JP6898625B2 (en) | 2019-04-19 | 2019-10-24 | Acid exhaust gas treatment agent, acid exhaust gas treatment method, and acid exhaust gas treatment equipment |
JP2019-193749 | 2019-10-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW202041464A true TW202041464A (en) | 2020-11-16 |
TWI809255B TWI809255B (en) | 2023-07-21 |
Family
ID=72936863
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW109108020A TWI809255B (en) | 2019-04-19 | 2020-03-11 | Acid exhaust treatment agent, acid exhaust treatment method and acid exhaust treatment equipment |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP6898625B2 (en) |
CN (1) | CN113660996B (en) |
TW (1) | TWI809255B (en) |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5114691A (en) * | 1990-01-18 | 1992-05-19 | Board Of Trustees Operating Michigan State University | Process using sorbents for the removal of SOx from flue gas |
CA2082639A1 (en) * | 1990-06-08 | 1991-12-09 | Terence William Turney | Ethylene sorbing substances |
US6028023A (en) * | 1997-10-20 | 2000-02-22 | Bulldog Technologies U.S.A., Inc. | Process for making, and use of, anionic clay materials |
AU2003243054A1 (en) * | 2003-07-07 | 2005-01-21 | Instituto Mexicano Del Petroleo | Method of obtaining multimetallic oxides derived from hydrotalcite-type compounds |
JP2007516073A (en) * | 2003-12-05 | 2007-06-21 | インターカット インコーポレイテッド | Mixed metal oxide adsorbent |
US9248426B2 (en) * | 2012-02-02 | 2016-02-02 | Samsung Electronics Co., Ltd. | Adsorbent for carbon dioxide, method of preparing the same, and capture module for carbon dioxide |
CN104071756B (en) * | 2014-06-24 | 2015-12-02 | 太原理工大学 | A kind of MnO 2the preparation method of intercalation hydrotalcite-like composite material |
EP3015429A1 (en) * | 2014-10-30 | 2016-05-04 | Wintershall Holding GmbH | Monolayer from at least one layered double hydroxide (LDH) |
JP2016190199A (en) * | 2015-03-31 | 2016-11-10 | 栗田工業株式会社 | Method for treating acidic exhaust gas generated from combustion facility, combustion facility and acidic exhaust gas treatment agent |
CN109046357A (en) * | 2018-08-27 | 2018-12-21 | 上海大学 | A kind of preparation method of metal oxide-LDH loaded catalyst |
-
2019
- 2019-10-24 JP JP2019193749A patent/JP6898625B2/en active Active
-
2020
- 2020-03-05 CN CN202080028089.6A patent/CN113660996B/en active Active
- 2020-03-11 TW TW109108020A patent/TWI809255B/en active
Also Published As
Publication number | Publication date |
---|---|
CN113660996A (en) | 2021-11-16 |
JP2020175376A (en) | 2020-10-29 |
TWI809255B (en) | 2023-07-21 |
JP6898625B2 (en) | 2021-07-07 |
CN113660996B (en) | 2024-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6173703B2 (en) | Carbon dioxide adsorbent, method for producing the same, and carbon dioxide capturing module including the same | |
JPH01503232A (en) | Reactive calcium hydroxide-based purification agent for purifying gas and waste gas and method for purifying gas and waste gas | |
JP4364798B2 (en) | Method for producing manganese compound and method for using the same | |
KR102558233B1 (en) | Acid exhaust gas treatment agent, acid exhaust gas treatment method, and acid exhaust gas treatment facility | |
KR100225473B1 (en) | Process for removing sulfur dioxide and nitrogen oxides from air stream | |
JP2012106215A (en) | Method for purification and treatment of flue gas | |
TWI809255B (en) | Acid exhaust treatment agent, acid exhaust treatment method and acid exhaust treatment equipment | |
CN110102009A (en) | A kind of method of catalysis oxidation rhodanide | |
CN115555004B (en) | Preparation and application of hydrotalcite-like compound-based composite hydrolysis catalyst for carbonyl sulfide removal | |
JPH0687943B2 (en) | Exhaust gas purification method | |
KR100225474B1 (en) | Method for removing sulfur dioxide and nitrogen oxides from combustion gases | |
KR102556856B1 (en) | Carbon dioxide absorbent and method for producing desul | |
EP3356574B1 (en) | Low temperature vapor phase digestion of graphite | |
CN1345621A (en) | Removing sulfur dioxide from industrial waste gas by ammonia regeneration circulation process | |
JPH1147536A (en) | Method for treating exhaust gas | |
TWI874728B (en) | Acid waste gas treatment method, acid waste gas treatment equipment and incineration facility | |
CN112403185B (en) | Method for recovering ferrous ammonium sulfite by using sintering flue gas | |
KR102556855B1 (en) | A Carbon Dioxide Absorbent | |
JPH08206445A (en) | Purification of exhaust gas | |
JP2702461B2 (en) | Exhaust gas purification method | |
CN109759072B (en) | Preparation method and application of a new type of self-supporting rare earth intercalation composite oxide catalyst | |
Fenouil et al. | Kinetic and structural studies of calcium-based sorbents for high-temperature coal-gas desulfurization | |
KR20250036415A (en) | Recovering method for radioactive carbon from wasted activated carbon and recovering system thereof | |
JP4491688B2 (en) | Production inhibitor and production inhibition method for chlorinated aromatic compounds | |
JPH11179143A (en) | Method for treating exhaust gas |