WO2022195953A1 - 酸性排ガスの処理方法、酸性排ガスの処理設備、及び、焼却施設 - Google Patents
酸性排ガスの処理方法、酸性排ガスの処理設備、及び、焼却施設 Download PDFInfo
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- WO2022195953A1 WO2022195953A1 PCT/JP2021/040840 JP2021040840W WO2022195953A1 WO 2022195953 A1 WO2022195953 A1 WO 2022195953A1 JP 2021040840 W JP2021040840 W JP 2021040840W WO 2022195953 A1 WO2022195953 A1 WO 2022195953A1
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- Prior art keywords
- exhaust gas
- layered double
- double hydroxide
- type
- acidic exhaust
- Prior art date
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- 230000002378 acidificating effect Effects 0.000 title claims abstract description 182
- 238000000034 method Methods 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 190
- 229910003023 Mg-Al Inorganic materials 0.000 claims abstract description 123
- 238000011282 treatment Methods 0.000 claims abstract description 74
- 230000001172 regenerating effect Effects 0.000 claims description 25
- -1 hydroxide ions Chemical class 0.000 claims description 21
- 150000001450 anions Chemical class 0.000 claims description 20
- 239000011229 interlayer Substances 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 description 180
- 238000001179 sorption measurement Methods 0.000 description 47
- 239000000047 product Substances 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000000126 substance Substances 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 25
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 25
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 25
- 239000000463 material Substances 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 22
- 238000011069 regeneration method Methods 0.000 description 19
- 230000008929 regeneration Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000003463 adsorbent Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 238000012546 transfer Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000012492 regenerant Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 150000001875 compounds 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
- 239000000203 mixture Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 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
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- B01D53/81—Solid phase processes
- B01D53/83—Solid phase processes with moving reactants
Definitions
- the present invention relates to a method for treating acidic exhaust gas, a facility for treating acidic exhaust gas, and an incineration facility.
- the flue gas emitted from the incinerator at the incineration facility contains acidic gas, which is a harmful acidic substance such as hydrogen chloride. Therefore, it is necessary to remove the acid gas before releasing the flue gas into the atmosphere.
- acidic exhaust gas combustion exhaust gas containing acidic gas.
- Patent Document 1 discloses a method for treating acidic exhaust gas generated in an incineration facility, in which acidic exhaust gas such as hydrogen chloride is treated by contacting the acidic exhaust gas generated in an incineration facility with a solid acidic exhaust gas treatment agent containing a layered double hydroxide. Have been described.
- the present invention is capable of reducing the amount of layered double hydroxide required for treating acidic exhaust gas, and is capable of regenerating the layered double hydroxide used for treating acidic exhaust gas.
- An object of the present invention is to provide a method for treating acidic exhaust gas, a facility for treating acidic exhaust gas, and an incineration facility that can suppress an increase in cost.
- the present inventors have made intensive studies to solve the above problems, and found that the above problems can be solved by treating acidic exhaust gas using an OH-type Mg—Al layered double hydroxide.
- the present invention provides the following [1] to [10].
- the OH-type Mg—Al layered double hydroxide used in the first step is obtained by exchanging the interlayer anion of the OH-type Mg—Al layered double hydroxide that has passed through with hydroxide ions.
- a facility for treating acidic exhaust gas comprising means for performing the method for treating acidic exhaust gas according to any one of [1] to [5] above.
- a first unit including a container for containing the OH-type Mg—Al layered double hydroxide used in the first step, and a first pipe for guiding acidic exhaust gas generated from a generation source to the container.
- a regenerating device for exchanging the interlayer anions of the OH-type Mg—Al layered double hydroxide that has passed through to hydroxide ions to generate a regenerated product, and the regenerated product from the regenerating device to the first unit.
- the second pipe guides the OH-type Mg—Al layered double hydroxide subjected to acidic exhaust gas treatment from the first unit to the regeneration device, and transfers the regenerated product from the regeneration device to the first
- An incineration facility comprising an incinerator and the acidic exhaust gas treatment facility according to any one of [6] to [9] above.
- the amount of layered double hydroxide required for treating acidic exhaust gas can be reduced, and the increase in cost when regenerating the layered double hydroxide used for treating acidic exhaust gas can be avoided. It is possible to provide a method for treating acidic exhaust gas, a facility for treating acidic exhaust gas, and an incineration facility that can reduce the amount of acid exhaust gas.
- FIG. 4 is a diagram schematically showing changes over time in the state of adsorption of a substance to be adsorbed when a fluid containing the substance to be adsorbed is passed through an adsorption tower filled with an adsorbent.
- FIG. 1(a) shows the temporal transition of the concentration gradient of the substance to be adsorbed inside the adsorption tower
- FIG. 1( b ) shows an arbitrary The adsorption rate of the adsorbent at the position is shown
- FIG. 1(c) shows the change over time of the concentration of the substance to be adsorbed at the outlet of the adsorption tower including after the breakthrough time (t B ) has elapsed.
- FIG. 1 is a schematic configuration diagram showing an example of an acidic waste gas treatment facility and an incineration facility according to an embodiment of the present invention
- FIG. 4 is a schematic diagram showing an example of the state of treatment, regeneration, and transfer of the layered double hydroxide in the first and second units and transition thereof during the first and second steps.
- FIG. 3 is a diagram showing breakthrough curves of Examples and Comparative Examples;
- a method for treating acidic exhaust gas according to an embodiment of the present invention is a method for treating acidic exhaust gas, and includes a first step of treating acidic gas in acidic exhaust gas using OH-type Mg—Al layered double hydroxide.
- the acidic exhaust gas generated from a source such as an incinerator is brought into contact with the OH-type Mg—Al layered double hydroxide to remove the hydrogen chloride contained in the acidic exhaust gas.
- a source such as an incinerator
- the above method for treating acidic exhaust gas has the following advantages due to the use of the OH-type Mg—Al layered double hydroxide as a treating agent for acidic exhaust gas.
- the OH-type Mg--Al layered double hydroxide has a higher hydrogen chloride adsorption rate than the CO 3 -type Mg--Al layered double hydroxide, which is known as a treatment agent for acidic exhaust gas.
- the reason for this is, but not limited to, that the reaction between the CO 3 type Mg—Al layered double hydroxide and hydrogen chloride causes OH ⁇ and CO 3 2 ⁇ in the interlayer water of the Mg—Al layered double hydroxide.
- OH-type Mg-Al layered double hydroxide not only the ion exchange reaction but also the acid-base reaction between OH - and H + in the interlayer water occurs. It is believed that there is.
- OH-type Mg-Al layered double hydroxide (hereinafter sometimes simply referred to as "recycled product") capable of treating acidic exhaust gas by regenerating OH-type Mg-Al layered double hydroxide that has passed through
- regenerant such as sodium hydroxide
- the carbonate required for regenerating the CO 3 type Mg-Al layered double hydroxide that has passed through is unnecessary.
- the cost involved in regenerating the layered double hydroxide can be reduced.
- the amount of OH-type Mg—Al layered double hydroxide required for treating acidic exhaust gas is small, the amount of regenerant required for regeneration is also small. Therefore, the initial cost can be greatly reduced, and the running cost can be greatly reduced in the facility for repeating the treatment of the acidic exhaust gas and the regeneration of the layered double hydroxide.
- the acidic exhaust gas generated from a source such as an incinerator is brought into contact with the OH-type Mg—Al layered double hydroxide to remove hydrogen chloride, sulfur oxides, nitrogen oxides, etc. in the acidic exhaust gas.
- Remove the acid gas component of The OH-type Mg—Al layered double hydroxide is a nanoparticle having a structure in which layered hydroxide basic layers and intermediate layers composed of interlayer anions and interlayer water are alternately laminated.
- the OH-type Mg—Al layered double hydroxide is, for example, in the form of chloride ions in the case of hydrogen chloride, in the form of sulfate ions in the case of sulfur oxides, and in the form of nitrate ions in the case of nitrogen oxides. , respectively, take in this component by exchanging with the intercalation anion, so that the acid gas component can be removed from the acidic exhaust gas.
- the gas to be treated is passed through a container containing nanoparticles of OH-type Mg-Al layered double hydroxide, and the gas to be treated is OH-type Mg-Al layered double hydroxide.
- the acid gas component can be removed by contacting with an object.
- the OH-type Mg-Al layered double hydroxide is more effective than the CO 3 -type Mg-Al layered double hydroxide, which is known as a treatment agent for acidic exhaust gas.
- the adsorption rate of hydrogen chloride is large. When a treating agent having a high adsorption rate is used, the amount of treating agent required for treating acidic exhaust gas is reduced, making it possible to design compact and economical treatment equipment. The reason is explained below.
- the time change in the adsorption rate of the substance to be adsorbed in the adsorption tower is the outlet of the adsorption tower (hereinafter referred to as , outlet of the tower).
- the substance to be adsorbed advances toward the tower outlet at a constant speed while having a concentration gradient of a certain width.
- the curve representing the change in the concentration of the target adsorption target over time at the outlet of the tower is called a "breakthrough curve".
- FIG. 1 shows a schematic diagram of the change over time in the state of adsorption of the target substance when a fluid containing the target substance is passed through the adsorption tower containing the above-described adsorbent (Eiji Ishizaki, Research on computer simulation of adsorption dynamics in adsorption towers, doctoral dissertation, graduate School of Science and Technology, Ibaraki University, September 2016, pp. 28-29).
- FIG. 1(a) shows the temporal transition of the concentration gradient of the substance to be adsorbed inside the adsorption tower
- FIG. 1(a) shows the temporal transition of the concentration gradient of the substance to be adsorbed inside the adsorption tower
- FIG. 1( b ) shows the entrance of the adsorption tower (hereinafter referred to as tower represents the adsorption rate of the adsorbent at an arbitrary position from the inlet ) to the tower outlet, and FIG. represents the change over time.
- tower represents the adsorption rate of the adsorbent at an arbitrary position from the inlet
- FIG. represents the change over time.
- FIG. 1(a) when a fluid containing a substance to be adsorbed at a constant concentration (C 0 ) is passed through an adsorption tower T at a constant flow rate, a stable substance concentration gradient ( The mass transfer zone (MTZ), hereinafter, forms an adsorption equilibrium zone E and proceeds downward toward the tower outlet Tb in FIG.
- the mass transfer zone (MTZ) hereinafter, forms an adsorption equilibrium zone E and proceeds downward toward the tower outlet Tb in FIG.
- t B the concentration of the substance to be adsorbed at the tower outlet Tb eventually reaches the concentration (C 0 ) with the lapse of time, as shown in FIG. 1(c). That is, FIG. 1(c) represents a breakthrough curve.
- FIG. 1(b) shows the adsorption rate (adsorption amount (q)/saturated adsorption amount (q 0 )) of the adsorbent at an arbitrary position from the tower inlet Ta to the tower outlet Tb at the breakthrough time (t B ). represent. That is, FIG. 1(b) represents the adsorption state inside the adsorption tower T when the breakthrough time (t B ) is reached.
- the curve showing the change in the adsorption rate (q/q 0 ) inside the adsorption tower T from the breakthrough time (t B ) to the time (t e ) when the amount of material adsorption inside the adsorption tower T reaches saturation is equal to the curve showing changes in the concentration (C) of the substance to be adsorbed at the tower outlet Tb or the ratio (C/C 0 ) of the concentration (C) to the concentration (C 0 ).
- the saturated adsorption amount of hydrogen chloride of the OH-type Mg--Al layered double hydroxide and the saturated adsorption amount of hydrogen chloride of the CO 3 -type Mg--Al layered double hydroxide are almost the same. Therefore, the amount of the OH-type Mg—Al layered double hydroxide, which has a high hydrogen chloride adsorption rate, can be made smaller than the amount of the CO 3 -type Mg—Al layered double hydroxide. It can be a compact and economical treatment facility.
- the OH-type Mg—Al layered double hydroxide used as an acidic exhaust gas treatment agent in the first step consists of a basic hydroxide layer ([Mg 2+ 1 ⁇ x Al 3+ x (OH) 2 ]) and an interlayer hydroxide It is a nanoparticle having a structure in which intermediate layers ([(OH ⁇ ) x ⁇ yH 2 O]) composed of ions and interlayer water are alternately laminated. It is a non-stoichiometric compound in which the hydroxide basic layer has a positive charge corresponding to x, and hydroxide ions are present in the intermediate layer as anions having a negative charge to compensate for this.
- the OH-type Mg--Al layered double hydroxide can incorporate acid gases such as hydrogen chloride, sulfur oxides and nitrogen oxides between the layers while maintaining the basic hydroxide layer. Therefore, it can be suitably used for acidic exhaust gas treatment for removing the above acidic gases.
- the OH-type Mg—Al layered double hydroxide has a particularly high adsorption rate of hydrogen chloride, so the OH-type Mg—Al layered double hydroxide necessary for the reaction with the acidic gas component in the acidic exhaust gas can reduce the amount of
- the OH-type Mg—Al layered double hydroxide includes naturally occurring clay minerals as meixnerite, but synthetic powder is usually used.
- the synthesis method is not particularly limited, and a known method (for example, the method described in Journal of Materials Science (2007) 42:9210-9215) can be used.
- the OH-type Mg--Al layered double hydroxide is obtained by regenerating the OH-type Mg--Al layered double hydroxide that has been subjected to acidic exhaust gas treatment. Inexpensive regenerants such as sodium hydroxide can then be used.
- layered double hydroxides other than the OH-type Mg-Al layered double hydroxide for example, calcium hydroxide (slaked lime), oxidized Chemicals other than layered double hydroxides such as calcium, sodium bicarbonate (sodium bicarbonate), sodium carbonate, dolomite hydroxide, light burnt dolomite, aluminum hydroxide, aluminum oxide, magnesium hydroxide and magnesium oxide may be used in combination.
- calcium hydroxide slaked lime
- oxidized Chemicals other than layered double hydroxides such as calcium, sodium bicarbonate (sodium bicarbonate), sodium carbonate, dolomite hydroxide, light burnt dolomite, aluminum hydroxide, aluminum oxide, magnesium hydroxide and magnesium oxide may be used in combination.
- the OH-type Mg—Al layered double hydroxide used in the first step may contain a regenerated product.
- the OH-type Mg—Al layered double hydroxide used in the first step preferably contains 90% by mass or more, more preferably 95% by mass or more, and still more preferably 99% by mass or more of the regenerated product. 100% by mass of the OH-type Mg—Al layered double hydroxide used in the first step may be a recycled product. Since the OH-type Mg-Al layered double hydroxide used in the first step contains a large amount of recycled products, the need to add new treatment agents and the need to dispose of used treatment agents is reduced, and the environment is improved. It becomes easier to reduce the load.
- the regenerated product may be one that has been regenerated in an external process, or one that has been generated in the second process described below.
- Using the recycle produced in the second step reduces the need to add new processing agents.
- the proportion of the regenerated material used in the first step can be increased. easier to do.
- the interlayer anions of the OH-type Mg—Al layered double hydroxide used for the treatment of the acidic exhaust gas are ion-exchanged with hydroxide ions to obtain the OH-type Mg—Al layered double hydroxide. It may further have a step of producing a regenerated product (hereinafter referred to as a second step).
- a second step a step of producing a regenerated product
- the interlayer hydroxide ions are exchanged with other anions derived from the acidic exhaust gas such as chlorine ions.
- the OH-type Mg—Al layered double hydroxide that has passed through to be regenerated is treated in the first step. It was offered to In this case, the OH-type Mg—Al layered double hydroxide used in the first step is regenerated and can be used again for acidic exhaust gas treatment, thus facilitating reduction of the environmental load.
- the first step and the second step are performed in the same equipment, so that the object to be reproduced is generated near the position where the reproduction is performed. The second step can be easily carried out without the need for long-distance transportation of the object, and it becomes easy to obtain a regenerated product with high purity.
- At least part of the regenerated product produced in the second step is used in the first step. If the recycled product produced in the second step is used in the first step, the need to add a new treatment agent is reduced, so the running cost when continuously treating acidic exhaust gas. becomes easier to reduce. At least part of the regenerated layered double hydroxide may be transferred outside the treatment facility and used in an external facility.
- the first step and the second step are set as one cycle, and the cycle is repeatedly performed, and the first step of any one of the second and subsequent cycles
- the regenerated product in the second step of the cycle before the cycle is used.
- the OH-type Mg—Al layered double hydroxide which is a treatment agent for acidic exhaust gas, can be used repeatedly while being regenerated, which makes it easier to further reduce running costs. Moreover, it becomes easy to continue acidic waste gas treatment for a long period of time.
- regenerating agent Sodium hydroxide, potassium hydroxide, etc., can be used as a regenerating agent for regenerating the OH-type Mg—Al layered double hydroxide that has passed through. These regenerating agents are less expensive than carbonates used as regenerating agents for the CO 3 type Mg—Al layered double hydroxide that has passed through, making it easier to reduce the cost required to regenerate the layered double hydroxide. .
- Regeneration of the OH-type Mg—Al layered double hydroxide that has been subjected to acidic exhaust gas treatment is performed by, for example, mixing and stirring with an aqueous sodium hydroxide solution having a concentration of 0.4% by mass or more at room temperature to 80° C. to generate ions. It can be done by exchanging
- the amount of the regenerant used in the second step is not particularly limited, but it is preferably 10 to 30 mass parts per 100 parts by mass of the OH-type Mg-Al layered double hydroxide that has passed through to be regenerated. parts, more preferably 10 to 20 parts by mass, still more preferably 10 to 15 parts by mass.
- the anions in the layered double hydroxide are replaced with hydroxide ions to regenerate the layered double hydroxide, and the hydrogen chloride, sulfuric acid, It is preferable to recover acidic substances such as nitric acid by a method of dissolving them in water.
- the recovered acidic substance can be reused as an industrial acidic substance or the like.
- the OH-type Mg-Al layered double hydroxide subjected to the acidic exhaust gas treatment in the first step may be replaced with unused OH-type Mg-Al layered double hydroxide or a regenerated product, or A fixed amount may be replaced in a batch manner, or may be replaced sequentially in a continuous manner.
- batch replacement there is an advantage that the OH-type Mg-Al layered double hydroxide is easy to effectively use, and in the case of continuous replacement, it is easy to continue acidic exhaust gas treatment and the configuration of equipment is simplified. It has the advantage of being easy.
- a plurality of routes each containing an OH-type Mg—Al layered double hydroxide are provided, and the acidic exhaust gas is selectively guided to one of these routes to be included in the route.
- a mode is adopted in which the OH-type Mg--Al layered double hydroxide contained in the other of the plurality of paths is regenerated while the acidic exhaust gas is brought into contact with the OH-type Mg--Al layered double hydroxide.
- the second step can be performed in parallel with the first step using a plurality of routes, so that the OH-type Mg—Al layered double hydroxide can be obtained while facilitating the continuation of the acidic exhaust gas treatment.
- Regeneration can also be carried out by supplying a regenerant to the layered double hydroxide contained in the non-regenerating pathway.
- the OH-type Mg—Al layered double hydroxide subjected to acidic exhaust gas treatment is continuously removed, or a predetermined amount is sequentially removed at a predetermined timing, and the removed layered double hydroxide is It is possible to adopt a mode in which the corresponding amount of regenerated material is supplied continuously or sequentially at a predetermined timing.
- a facility for treating acidic exhaust gas has means for performing the above-described method for treating acidic exhaust gas.
- means for carrying out the first step include, for example, a container containing the OH-type Mg—Al layered double hydroxide used in the first step, and an incinerator or the like. and a first line for directing the acidic exhaust gas generated from the source to the vessel.
- this unit will be referred to as a "first unit".
- the first pipe constitutes part of the flue through which the gas to be processed flows.
- upstream Downstream
- upstream Downstream
- downstream upstream
- downstream downstream
- inlet inlet
- outlet refer to the direction in which the gas to be treated flows.
- the first step described above is performed by introducing the acidic exhaust gas discharged from the source such as the incinerator into the inlet of the first unit.
- acid gas components such as hydrogen chloride are sufficiently removed as described above.
- the treated gas from which the acidic gas component has been removed is discharged from the outlet of the first unit.
- a regenerating device for generating a regenerated product by exchanging interlayer anions of the OH-type Mg—Al layered double hydroxide that has passed through into hydroxide ions, and the above and a second pipe for guiding the regenerated product from the regenerator to the first unit.
- this unit will be referred to as a "second unit”.
- the second pipe guides the OH-type Mg—Al layered double hydroxide subjected to acidic exhaust gas treatment from the first unit to the regenerator, and the regenerated product from the regenerator to the first unit. It can be a guide.
- the end of the second pipe connected to the first unit is the inlet of the used layered double hydroxide and the outlet of the regenerated product
- the end of the second pipe connected to the regenerator is the used It is the outlet of the layered double hydroxide and the inlet of the regenerated material.
- the second unit may include an extruding member such as a screw disposed in at least one of the vicinity of the second pipe and the inside of the second pipe.
- the layered double hydroxide can be transferred from the first unit to the second unit or from the second unit to the first unit by pushing the layered double hydroxide with the extrusion member, such as by rotating the screw.
- the regeneration device of the second unit may be configured to receive the OH-type Mg-Al layered double hydroxide that has passed through from the outside.
- the used layered double hydroxide generated in other treatment facilities can be used as a raw material for producing the recycled product, making it easier to secure the raw material.
- the first unit includes a plurality of containers each containing an OH-type Mg—Al layered double hydroxide, and selectively directs acidic exhaust gas generated from a source such as an incinerator to any one of the plurality of containers.
- a switching valve for directing may also be provided. By providing the switching valve, when the processing capacity of the acidic exhaust gas by the anion-type layered double hydroxide housed in one of the plurality of containers is reduced, the switching valve allows the other container to switch By introducing the gas, the OH-type Mg—Al layered double hydroxide contained in the container, whose processing capacity for acidic exhaust gas is not reduced, continues to treat acidic exhaust gas without lowering its processing capacity. can do.
- the acidic exhaust gas treatment facility may further include a concentration detection device arranged downstream of the first unit for continuously detecting the concentration of hydrogen chloride in the acidic exhaust gas discharged from the first unit. good.
- concentration detection device By providing the concentration detection device, it is possible to grasp the increase in the concentration of hydrogen chloride in the gas. Then, as described above, when adopting a configuration in which a plurality of anion-type layered double hydroxides are stored in a plurality of containers via switching valves, the switching valves allow the containers with reduced hydrogen chloride processing efficiency to By switching to another container in which the treatment efficiency is not lowered, the treatment of the acidic exhaust gas can be continued without lowering the treatment capacity.
- An incineration facility includes an incinerator and equipment for treating acidic exhaust gas.
- the acidic exhaust gas treatment equipment is installed downstream of the incinerator, takes in the acidic exhaust gas discharged from the incinerator, and treats the acidic exhaust gas by executing the first step described above.
- the acidic gas component in the acidic exhaust gas generated from the incinerator is removed by the above treatment equipment, so it is possible to prevent release of harmful acidic substances to the surrounding environment.
- the acidic exhaust gas treatment facility is equipped with a second unit that performs the second step described above, the used OH-type Mg—Al produced in the first unit that performs the first step A layered double hydroxide can be regenerated. Therefore, by reusing the obtained regenerated product in the first unit, it is possible to continue the treatment of the acidic exhaust gas efficiently. It is also possible to use the recycled product produced in the second unit in other processing equipment.
- FIG. 2 is a schematic configuration diagram showing an example of an incineration facility including equipment for treating acidic exhaust gas according to an embodiment of the present invention. The invention is not restricted to the configuration shown.
- the incineration facility 100 shown in FIG. 2 includes an incinerator 11, a boiler 12, a gas cooling device 13, a dust collector 14, an induced draft air 15 and a chimney 16, and pipes 21 to 21 that sequentially connect these to form a flue. 26.
- the incineration facility 100 includes a unit 50 including a container for storing the OH-type Mg—Al layered double hydroxide, which is an acidic exhaust gas treatment agent, and the interlayer anion of the OH-type Mg—Al layered double hydroxide that has passed through. and a unit 60 including a regenerator 40 for exchanging hydroxide ions to produce a regenerated product.
- the unit 50 composed of the container 31 containing the OH-type Mg—Al layered double hydroxide and the piping 24 for guiding the acidic exhaust gas generated from the incinerator 11 to the container 31 is described above.
- a first unit for performing a first step the intermediate anions of the anion-type Mg—Al layered double hydroxide that has passed through are exchanged with hydroxide ions to produce a regenerated product, and the first unit 50 is used to treat the acidic exhaust gas.
- a unit 60 including a pipe 41 for guiding the anionic Mg—Al layered double hydroxide to the regenerator 40 and for guiding the regenerated product from the regenerator 40 to the first unit 50 performs the above-described second step. It is the second unit.
- the operation of the incineration facility 100 including the acidic exhaust gas treatment equipment 80 will be described.
- the acidic exhaust gas generated in the incinerator 11 is heat-recovered by the boiler 12, cooled by the cooling device 13, collected by the dust collector 14, and guided to the first unit 50 of the acidic exhaust gas treatment facility 80.
- the OH-type Mg—Al layered double hydroxide housed in the container 31 is in a state where the treatment capacity is not lowered, and has not been subjected to treatment of acidic exhaust gas even once after synthesis. There are none, regenerated products that have been subjected to the treatment of acidic exhaust gas one or more times, or mixtures thereof.
- the first step described above is performed on the acidic exhaust gas in the first unit.
- acidic gas components such as hydrogen chloride, sulfur oxides, and nitrogen oxides in the acidic exhaust gas are removed.
- the gas from which the treatment has been completed and the acidic gas components have been removed is discharged from the first unit 50, passes through the induced draft fan 15, and is discharged to the outside from the chimney 16.
- the OH-type Mg-Al layered state subjected to the acidic exhaust gas treatment is placed in the container 31 of the first unit 50. Transfer the double hydroxide to the second unit 60 . Then, a regenerated OH-type Mg—Al layered double hydroxide is produced in the regeneration device 40, and the regenerated material is transferred from the second unit 60 to the first unit at a predetermined timing.
- a flow meter is provided to measure the flow rate of the acidic exhaust gas to be treated, and the flow rate measured by the flow meter and the elapsed time The transfer may be performed based on Alternatively, a concentration detection device for continuously detecting the concentration of acidic gas components in the acidic exhaust gas discharged from the first unit 50 is provided on the downstream side of the first unit 50, and based on the detection result, the second Transfer of the layered double hydroxide from one unit 50 to the second unit 60 may be performed.
- the first unit includes a plurality of containers each containing an OH-type Mg—Al layered double hydroxide, and the acidic exhaust gas generated from the incinerator is discharged into one of the plurality of containers.
- the switching valve may be controlled based on the detection result of the concentration detection device.
- FIG. 3 is a schematic diagram showing an example of the state of treatment, regeneration, and transfer of the layered double hydroxide in the first and second units and its transition during the first and second steps.
- the second unit has a storage space that is at least twice the volume of the container of the first unit, and the used layered double hydroxide is replaced with the regenerated product all at once. described as a thing.
- the timing of transfer of the layered double hydroxide is different from that shown in FIG. 3, it is clear that the transition is substantially the same as in FIG. Therefore, detailed description is omitted.
- FIG. 3(a) shows the initial stage, and inside the first unit 50, the synthesized unused OH-type Mg—Al layered double hydroxide is accommodated.
- a regenerated product that is produced outside and capable of treating the acidic exhaust gas may be accommodated, or a mixture of the synthesized product and the regenerated product may be accommodated.
- a recycled OH-type Mg—Al layered double hydroxide capable of treating acidic exhaust gas is accommodated, and a used OH-type Mg—Al layered double hydroxide is stored. There is space available to receive them.
- the regenerated material in the second unit 60 is assumed to be generated outside, but the material subjected to acidic exhaust gas treatment in the first unit 50 is stored in the second unit 60 in advance. It can be anything you have.
- the OH-type Mg—Al layered double hydroxide By performing acidic exhaust gas treatment in the first unit 50, acidic exhaust gas components are incorporated into the OH-type Mg—Al layered double hydroxide, and in FIG. 3B, the OH-type Mg—Al layered double hydroxide is This indicates that the gas has been subjected to acidic exhaust gas treatment and is in a breakthrough or near-breakthrough state.
- the layered double hydroxide that is in a breakthrough or near-breakthrough state and is not suitable for acidic exhaust gas treatment is referred to as a "breakthrough material".
- the passed-through material in the first unit 50 is transferred to the empty space in the second unit 60. Then, as shown in FIG.
- the regenerated OH-type Mg—Al layered double hydroxide was transferred from the second unit 60 to the first unit 50, and transferred to the second unit 60. Recycle the waste material.
- the recycled material generated by the second unit 60 is the recycled material transferred from the first unit 50, so in FIG. and described.
- FIG. 3(e) the recycled material in the first unit 50 changes to the permeated material
- the passed-through material is transferred from the first unit 50 to the empty space generated in the second unit 60 at the stage of FIG. 3(d).
- the self-recycled material in the second unit 60 is transferred to the first unit 50, and the self-recycled material is generated from the passing-through material in the second unit 60.
- FIG. FIGS. 3(a) to 3(d) are the first cycle
- FIGS. 3(d) to 3(g) are the second cycle
- FIG. 3(g) and subsequent cycles are the third and subsequent cycles.
- the self-regenerated material regenerated in the second cycle is used in the third cycle for acidic exhaust gas treatment.
- the first unit includes a plurality of containers each containing an OH-type Mg—Al layered double hydroxide, and the acidic exhaust gas generated from the incinerator is selectively transferred to any one of the plurality of containers.
- the layered double hydroxide contained in the container separated from the flue can be regenerated by the above-described regeneration method by operating the switching valve. . Therefore, it is possible to continue the treatment of the acidic exhaust gas in parallel with transferring the permeated matter to the regeneration device and performing the regeneration treatment.
- a plurality of containers and a switching valve are provided, it is not always necessary to transfer the layered double hydroxide from the container to the regenerating device. can be
- the recycled material produced by the second unit 60 may be used in treatment facilities other than the treatment facility 80 or in incineration facilities other than the incineration facility 100 .
- unused layered double hydroxide and a regenerated product produced outside are used. You may make it replenish suitably.
- the second unit 60 for regenerating the layered double hydroxide is provided in the INSIGHT of the incineration facility 100, but is not limited to this. 100 may be located off-site.
- means for taking out the layered double hydroxide that has been subjected to the treatment of the acidic exhaust gas from the first unit 60, layered double hydroxide that has not yet been subjected to treatment, and regenerated layered double hydroxide are preferably provided. Each of the above means may supply or take out the layered double hydroxide according to the flow rate of the acidic exhaust gas and/or the concentration of the acidic gas component.
- Example 1 A glass reaction tube with an inner diameter of 16 mm is filled with 0.1 g of OH-type Mg-Al layered double hydroxide, nitrogen gas is circulated from the upstream of the reaction tube, and the gas temperature at which each reaction tube is circulated in a tubular electric furnace. was adjusted to 170°C. While circulating nitrogen so that hydrogen chloride becomes 1,000 ppm, the flow rate of each gas is adjusted with a mass flow controller, and the above mixed gas is introduced into the reaction tube so that the superficial velocity in the reaction tube is 1.0 m / min. passed through. After the start of the test, the concentration of hydrogen chloride in the gas flowing through the outlet of the reaction tube was continuously measured with an FT-IR gas analyzer to create a breakthrough curve.
- the chemical formula of the OH-type Mg—Al layered double hydroxide used in Example 1 is as follows (molecular weight: 118.86). [Mg 0.67 Al 0.33 (OH) 2 ](OH ⁇ ) 0.33 ⁇ 3H 2 O Formula (1)
- This mixed solution was added dropwise to an aqueous sodium carbonate solution having a concentration of 0.1 mol/L while stirring at 30°C. At this time, the pH was maintained at 10.5 by dropping an aqueous sodium hydroxide solution having a concentration of 1.25 mol/L. After completion of the dropwise addition, the mixture was stirred at 30°C for 1 hour.
- Example 1 using the OH-type Mg—Al layered double hydroxide is better than Comparative Example 1 using the CO 3 -type Mg—Al layered double hydroxide.
- the breakthrough time is long, and the change in hydrogen chloride concentration after breakthrough is large.
- each hydrogen chloride tested in Example 1 and Comparative Example 1 The saturated adsorption amount was 0.101 g/g for the OH-type Mg—Al layered double hydroxide of Example 1, and 0.098 g/g for the CO 3 -type Mg—Al layered double hydroxide of Comparative Example 1. g, and both values are almost the same. From this, when the breakthrough time of the adsorption tower is designed to be constant, Example 1 using the OH-type Mg-Al layered double water oxide is more likely to produce the CO 3 -type Mg-Al layered double hydroxide.
- the layered double hydroxide after being ion-exchanged with chlorine ions is represented by the following chemical formula (5).
- [M 0.67 Al 0.33 (OH) 2 ](Cl ⁇ ) 0.33 ⁇ 3H 2 O Formula (5) Then, the compound of the above chemical formula (5) is converted into the layered double hydroxide of the above chemical formula (1) using sodium hydroxide as a regenerating agent, and the layered double hydroxide of the above chemical formula (3) using sodium carbonate as a regenerating agent.
- the regeneration reaction equations for each regeneration are represented by the following equations (6) and (7).
- Incinerator 12 Boiler 13: Gas cooler 14: Dust collector 15: Induced ventilator 16: Chimneys 21 to 23, 25, 26: Piping (flue) 24: First pipe 31: Layered double hydroxide container 40: Regeneration device 41: Second pipe 50: First unit 60: Second unit 80: Acid exhaust gas treatment facility 100: Incineration facility
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Abstract
Description
また、酸性排ガスの処理剤として知られているCO3型Mg-Al層状複水酸化物の場合、酸性排ガスの処理に供した後、再生のために用いる再生剤として、高価な炭酸塩を使用しなければならないという課題があった。高価な再生剤の使用はイニシャル及びランニングのコスト増加につながり、上述したように層状複水酸化物の使用量が多い場合はこの問題が顕著であった。
すなわち、本発明は、以下の[1]~[10]を提供するものである。
[1]酸性排ガスの処理方法であって、OH型Mg-Al層状複水酸化物を用いて、酸性排ガス中の酸性ガスを処理する第1の工程を有する、酸性排ガスの処理方法。
[2]前記第1の工程で使用するOH型Mg-Al層状複水酸化物は、破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンに交換して得られる再生物を含む、上記[1]に記載の酸性排ガスの処理方法。
[3]破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンにイオン交換して、OH型Mg-Al層状複水酸化物の再生物を生成する第2の工程を更に有し、
前記第1の工程では、前記第2の工程で生成した前記再生物の少なくとも一部を使用する、上記[1]又は[2]に記載の酸性排ガスの処理方法。
[4]破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンにイオン交換して、OH型Mg-Al層状複水酸化物の再生物を生成する第2の工程を更に有し、
前記第2の工程においては、前記第1の工程で酸性排ガス処理に供したOH型Mg-Al層状複水酸化物を用いて前記再生物を生成する、上記[1]又は[2]に記載の酸性排ガスの処理方法。
[5]破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンにイオン交換して、OH型Mg-Al層状複水酸化物の再生物を生成する第2の工程を更に有し、
前記第1の工程及び前記第2の工程を1サイクルとして、当該サイクルを繰り返し実行し、
2回目以降のいずれかのサイクルの前記第1の工程で用いられるOH型Mg-Al層状複水酸化物の少なくとも一部として、当該サイクル以前のサイクルの第2工程で再生した再生物を用いる、上記[1]又は[2]に記載の酸性排ガスの処理方法。
[6]上記[1]~[5]のいずれか一つに記載の酸性排ガスの処理方法を行う手段を有する、酸性排ガスの処理設備。
[7]前記第1の工程で用いるOH型Mg-Al層状複水酸化物を収容する容器と、発生源から発生する酸性排ガスを前記容器に導くための第1の配管とを含む第1ユニットを有する、上記[6]に記載の酸性排ガスの処理設備。
[8]破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンに交換して再生物を生成する再生装置と、前記再生装置から前記再生物を前記第1ユニットに導くための第2の配管とを含む第2ユニットを更に有する、上記[7]に記載の酸性排ガスの処理設備。
[9]前記第2の配管は、前記第1ユニットから酸性排ガス処理に供したOH型Mg-Al層状複水酸化物を前記再生装置に導くとともに、前記再生装置から前記再生物を前記第1ユニットに導く、上記[8]に記載の酸性排ガスの処理設備。
[10]焼却炉と、上記[6]~[9]のいずれか一つに記載の酸性排ガスの処理設備と、を有する焼却施設。
本発明の実施形態に係る酸性排ガスの処理方法は、酸性排ガスの処理方法であって、OH型Mg-Al層状複水酸化物を用いて、酸性排ガス中の酸性ガスを処理する第1の工程を有する。
上記酸性排ガスの処理方法には、酸性排ガスの処理剤としてOH型Mg-Al層状複水酸化物を用いていることにより、以下のような利点がある。
そして、塩化水素の吸着速度が大きいことにより、酸性排ガス中の酸性ガス成分との反応に必要なOH型Mg-Al層状複水酸化物の量が少なくて済む。このため、酸性排ガスの処理設備の規模を小さくすることができる。
また、破過したOH型Mg-Al層状複水酸化物を再生して、酸性排ガスの処理が可能なOH型Mg-Al層状複水酸化物(以下、単に「再生物」ということがある)を得るためには、水酸化ナトリウムなどの安価な再生剤を使用すればよく、破過したCO3型Mg-Al層状複水酸化物の再生に必要とされる炭酸塩を不要とすることができる。これにより、層状複水酸化物の再生に関わるコストを低減することができる。
加えて、上述したように、酸性排ガスの処理に必要なOH型Mg-Al層状複水酸化物の量が少ないため、再生に必要な再生剤の使用量も少なくなる。このため、イニシャルコストを大きく低減することができ、酸性排ガスの処理と層状複水酸化物の再生とを繰り返す設備においてはランニングコストも大きく低減することができる。
上記第1の工程においては、焼却炉等の発生源から発生する酸性排ガスをOH型Mg-Al層状複水酸化物に接触させて、酸性排ガス中の塩化水素、硫黄酸化物、窒素酸化物等の酸性ガス成分を除去する。
OH型Mg-Al層状複水酸化物は、層状の水酸化物基本層と、層間アニオン及び層間水からなる中間層が交互に積層した構造を有するナノ粒子である。そして、OH型Mg-Al層状複水酸化物は、例えば、塩化水素であれば塩素イオンの形で、硫黄酸化物であれば硫酸イオンの形で、窒素酸化物であれば硝酸イオンの形で、それぞれ層間アニオンと交換することによってこの成分を取り込むため、酸性排ガスから酸性ガス成分を除去することができる。
上述したように、OH型Mg-Al層状複水酸化物は、酸性排ガスの処理剤として知られているCO3型Mg-Al層状複水酸化物に比べて酸性排ガス中の酸性ガス成分、特に、塩化水素の吸着速度が大きい。そして、吸着速度が大きい処理剤を用いた場合、酸性排ガスの処理に必要な処理剤の量が少なくなり、コンパクトで経済的な処理設備を設計することが可能になる。その理由を以下に説明する。
吸着材が充填されている吸着塔に一定濃度の吸着対象物質を含む気体を一定流速で流した場合、吸着対象物質は吸着材によって吸着塔の入口側から順次吸着される。吸着塔内では、吸着対象物質は一定幅の濃度勾配を持ちながら、塔出口に向かって一定速度で進行する。吸着対象物質の濃度勾配の先端が塔出口に達する時間(破過時間)が経過した後の、塔出口における吸着対象物質濃度の経時変化を表す曲線は「破過曲線」と呼ばれ、吸着塔の設計に重要な要素となる。
第1の工程で酸性排ガス処理剤として用いられるOH型Mg-Al層状複水酸化物は、水酸化物基本層([Mg2+ 1-xAl3+ x(OH)2])と、層間水酸化物イオン及び層間水から構成される中間層([(OH-)x・yH2O])とが交互に積層した構造を有しているナノ粒子である。水酸化物基本層がx相当分の正電荷を持ち、これを補償する負電荷を持つ陰イオンとして水酸化物イオンが中間層に存在している不定比化合物である。
OH型Mg-Al層状複水酸化物は、水酸化物基本層を保持したまま、塩化水素、硫黄酸化物、窒素酸化物等の酸性ガスを層間に取り込むことができる。このため、上記の酸性ガスを除去する酸性排ガス処理に好適に用いることができる。
上述したように、OH型Mg-Al層状複水酸化物は、塩化水素の吸着速度が特に大きいので、酸性排ガス中の酸性ガス成分との反応に必要なOH型Mg-Al層状複水酸化物の量を少なくすることができる。
また、後述するように、OH型Mg-Al層状複水酸化物は、酸性排ガス処理に供したOH型Mg-Al層状複水酸化物を再生することにより得られる。このとき、水酸化ナトリウムなどの安価な再生剤を使用することができる。このため、OH型Mg-Al層状複水酸化物として、再生物又は再生物を含むものを用いることにより、CO3型Mg-Al層状複水酸化物等の他のアニオン型Mg-Al層状複水酸化物に比べてコスト上昇を抑制しやすくなる。
第1の工程で用いるOH型Mg-Al層状複水酸化物は、好ましくは90質量%以上、より好ましくは95質量%以上、更に好ましくは99質量%以上の再生物を含む。第1の工程で用いるOH型Mg-Al層状複水酸化物の100質量%が再生物であってもよい。第1の工程で用いるOH型Mg-Al層状複水酸化物が再生物を多く含むことで、新しい処理剤を追加する必要性や、使用済みの処理剤を廃棄する必要性が低下し、環境負荷を低減しやすくなる。
上記酸性排ガスの処理方法は、酸性排ガスの処理に供したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンにイオン交換して、OH型Mg-Al層状複水酸化物の再生物を生成する工程(以下、第2の工程という)を更に有していてもよい。
酸性排ガス処理に供したOH型Mg-Al層状複水酸化物は、前記酸性ガス成分が層間に取り込まれると、層間水酸化物イオンが、塩素イオン等の酸性排ガス由来の他のアニオンに交換され、破過したOH型Mg-Al層状複水酸化物となる。破過したOH型Mg-Al層状複水酸化物は、酸性排ガスを更に除去する能力を有しない。このため、上記第2の工程において、再度アニオン交換することにより、酸性排ガス処理可能なOH型Mg-Al層状複水酸化物に再生して、再度酸性排ガスの処理に利用することができる。
この場合、第1の工程で使用されたOH型Mg-Al層状複水酸化物が再生されて、再度酸性排ガス処理に利用できるので、環境負荷を低減しやすくなる。
また、後述する処理設備のように、上記第1の工程と第2の工程とが同じ設備内で実施されることにより、再生の対象物が再生を行う位置の近傍で生成されるので、再生の対象物を遠距離移送する必要がなく、第2の工程を容易に実施することができ、純度の高い再生物を得やすくなる。
上記第2の工程で生成された再生物を、上記第1の工程で使用すれば、新たな処理剤を追加する必要性が低下するため、継続的に酸性排ガスの処理を行う場合のランニングコストを低減しやすくなる。
なお、再生された層状複水酸化物の少なくとも一部を、処理設備外に移して外部の設備で利用するようにしてもよい。
本態様においては、酸性排ガスの処理剤であるOH型Mg-Al層状複水酸化物を再生しながら繰り返し利用することができるので、ランニングコストを更に低減させやすくなる。また、酸性排ガス処理を長期間継続しやすくなる。
本態様において、再生回数が予め定めた上限に達した場合は、未使用の合成品に入れ替えるようにしてもよい。また、酸性排ガスの処理性能を高く保つために、所定のタイミングで所定量の未使用の合成品を追加するようにしてもよい。
破過したOH型Mg-Al層状複水酸化物を再生するために用いる再生剤としては、水酸化ナトリウム、水酸化カリウム等が挙げられる。これらの再生剤は、破過したCO3型Mg-Al層状複水酸化物の再生剤として用いられる炭酸塩に比べて安価であり、層状複水酸化物の再生に要するコストを低減しやすくなる。
上記第1の工程において酸性排ガス処理に供したOH型Mg-Al層状複水酸化物は、未使用のOH型Mg-Al層状複水酸化物や再生物に、一括で置き換えてもよいし、バッチ式で一定量を置き換えてもよいし、連続的に順次置き換えてもよい。
一括で置き換える場合は、OH型Mg-Al層状複水酸化物を有効に利用しやすいという利点があり、連続的に置き換える場合は、酸性排ガス処理を継続させやすいことや、設備の構成を簡素化しやすい等の利点がある。
バッチ式で置き換える場合は、例えば、OH型Mg-Al層状複水酸化物をそれぞれ含む複数の経路を設け、それらのうちのいずれかの経路に酸性排ガスを選択的に導き、当該経路に含まれるOH型Mg-Al層状複水酸化物に酸性排ガスを接触させている間に、上記複数の経路のうちの他の経路に含まれるOH型Mg-Al層状複水酸化物を再生する態様を採ることができる。この場合、複数の経路を用いて、上記第2の工程を第1の工程と並行して実行することができるので、酸性排ガス処理を継続させやすくしつつ、OH型Mg-Al層状複水酸化物を有効に利用しやすくなる。
なお、上述したように、OH型Mg-Al層状複水酸化物を含む複数の経路を選択的に利用する場合、必ずしも容器から再生装置へ移送する必要はなく、酸性排ガス処理のために選択されていない経路に含まれる層状複水酸化物に再生剤を供給することによって再生を行うこともできる。
本発明の実施形態に係る酸性排ガスの処理設備は、上記の酸性排ガスの処理方法を行う手段を有する。
上記酸性排ガスの処理設備において、上述した第1の工程を実施する手段としては、例えば、上記第1の工程で用いるOH型Mg-Al層状複水酸化物を収容する容器と、焼却炉等の発生源から発生する酸性排ガスを上記容器に導くための第1の配管とを含むユニットが挙げられる。以下、当該ユニットを「第1ユニット」と称する。
この場合、上記第2の配管の第1ユニットへ接続する側の端部が、使用済み層状複水酸化物の入口かつ再生物の出口であり、再生装置へ接続する側の端部が使用済み層状複水酸化物の出口かつ再生物の入口である。
このように第2の配管を介して使用済み層状複水酸化物の受取りと再生物の送出しを行うようにすると、層状複水酸化物を繰り返し使用することができ、かつ、処理設備の構成を簡素にすることができる。
上記切換え弁を備えることにより、複数の容器のうちの一つに収容されたアニオン型層状複水酸化物による酸性排ガスの処理能力が低下した場合に、上記切換え弁によって、他の他方の容器へガスを導くことにより、当該容器内に収容された、酸性排ガスの処理能力が低下していないOH型Mg-Al層状複水酸化物によって、処理能力を低下させることなく、酸性排ガスの処理を継続することができる。
上記濃度検知装置を備えることにより、ガス中の塩化水素の濃度の上昇を把握することができる。そして、上述したように、切換え弁を介して複数の容器にアニオン型層状複水酸化物を収容した構成を採用している場合は、切換え弁によって、塩化水素の処理効率が低下した容器を、処理効率が低下していない別の容器に切り換えることで、処理能力を低下させることなく、酸性排ガスの処理を継続することができる。
本発明の実施形態に係る焼却施設は、焼却炉と、上記酸性排ガスの処理設備とを有する。
上記酸性排ガスの処理設備は、焼却炉の下流に設置され、焼却炉から排出される酸性排ガスを取込み、上述した第1の工程を実行することによって酸性排ガスを処理する。本焼却施設においては、焼却炉から発生する酸性排ガス中の酸性ガス成分が上記処理設備によって除去されるので、周辺環境に有害な酸性物質が放出されることを防止することができる。
また、酸性排ガスの処理設備が上述した第2の工程を実行する第2ユニットを備えたものであれば、第1の工程を実行する第1ユニットで生成された使用済みのOH型Mg-Al層状複水酸化物を再生することができる。このため、得られた再生物を第1ユニットで再利用することにより、効率的に酸性排ガスの処理を継続することができる。また、第2ユニットで生成された再生物を他の処理設備で利用することもできる。
以下、酸性排ガスの処理設備を含む焼却施設の具体例について図面を用いて説明する。
図2は、本発明の実施形態に係る酸性排ガスの処理設備を含む焼却施設の一例を示す模式的な構成図である。本発明は図示した構成には制限されない。
また、焼却施設100は、酸性排ガス処理剤であるOH型Mg-Al層状複水酸化物を収納する容器を含むユニット50と、破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンに交換して再生物を生成する再生装置40を含むユニット60と、を有する酸性排ガスの処理設備80を備えている。
また、破過したアニオン型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンに交換して再生物を生成する再生装置40、及び、第1ユニット50から酸性排ガスの処理に供したアニオン型Mg-Al層状複水酸化物を再生装置40に導くとともに、再生装置40から再生物を第1ユニット50に導くための配管41を含むユニット60が、上述した第2の工程を実行する第2ユニットである。
次に、酸性排ガス処理設備80を含む焼却施設100の動作を説明する。
まず、焼却炉11で発生した酸性排ガスは、ボイラ12で熱回収され、冷却装置13で冷却された後、集塵機14で集められて、酸性排ガス処理設備80の第1ユニット50へと導かれる。なお、初期状態では、容器31に収容されているOH型Mg-Al層状複水酸化物は、処理能力が低下していない状態のものであり、合成後に一度も酸性排ガスの処理に供されていないもの、一度以上酸性排ガスの処理に供された後に再生された再生物、又は、これらの混合物である。
そして、上記酸性排ガスに対して、第1ユニットにおいて、上述した第1の工程が実行される。これによって、酸性排ガス中の塩化水素、硫黄酸化物、及び、窒素酸化物等の酸性ガス成分が除去される。
処理が終了し酸性ガス成分が除去されたガスは、第1ユニット50から排出され、誘因通風機15を経て煙突16から外部へ放出される。
そして、再生装置40にてOH型Mg-Al層状複水酸化物の再生物を生成し、所定のタイミングで第2ユニット60から第1ユニットへ再生物を移送する。
あるいは、第1ユニット50の下流側に、第1ユニット50から排出される酸性排ガス中の酸性ガス成分の濃度を連続的に検知する濃度検知装置を設けておき、その検知結果に基づいて、第1ユニット50から第2ユニット60への層状複水酸化物の移送を実行してもよい。
また、上述したように、上記第1ユニットとして、OH型Mg-Al層状複水酸化物をそれぞれ収容する複数の容器を含み、焼却炉から発生する酸性排ガスを、上記複数の容器のいずれかに選択的に導くための切換え弁を更に備えているものとする場合は、上記濃度検知装置の検知結果に基づいて、切換え弁を制御するようにしてもよい。
図3においては、理解を容易にするため、第2ユニットが第1ユニットの容器の倍以上の容積の収容スペースを有しており、使用済みの層状複水酸化物を一括で再生物に置き換えるものとして説明する。なお、バッチ式や連続式で再生物へ置き換える場合は、層状複水酸化物の移送のタイミングが図3に示したものと異なるものの、実質的に図3と同様に遷移することが明らかであるため、詳細な説明は省略する。
次に、図3(c)に示すように、第1ユニット50内の破過物を第2ユニット60内の空きスペースに移送する。そして、図3(d)の段階へ遷移する間に、OH型Mg-Al層状複水酸化物の再生物を第2ユニット60から第1ユニット50へ移送するとともに、第2ユニット60に移送した破過物の再生を行う。なお、図3(d)の段階において、第2ユニット60によって生成された再生物は、第1ユニット50から移送された破過物を再生したものであるため、図3では「自己再生物」と記載する。
そして、図3(f)の段階において、上記図3(d)の段階で第2ユニット60内に生じた空きスペースに、第1ユニット50から破過物を移送する。そして、図3(g)へ遷移する間に、第2ユニット60内の自己再生物を第1ユニット50へ移送するとともに、第2ユニット60内の破過物から自己再生物を生成する。
図3(a)~図3(d)が第1サイクル、図3(d)~図3(g)が第2サイクル、図3(g)以降が第3サイクル以降のサイクルである。図3に示す例では、第2サイクルで再生された自己再生物が第3サイクルで酸性排ガス処理に用いられている。
上述したように、上記第1ユニットが、OH型Mg-Al層状複水酸化物をそれぞれ収容する複数の容器を含み、焼却炉から発生する酸性排ガスを、上記複数の容器のいずれかに選択的に導くための切換え弁を更に備えている場合、上記切換え弁を作動させることによって、煙道から切り離された方の容器に含まれる層状複水酸化物を上述した再生方法によって再生することができる。このため、破過物を再生装置へ移送して再生処理を行うのと並行して、酸性排ガスの処理を継続することができる。
また、上記複数の容器と切換え弁を備えている場合、必ずしも容器から層状複水酸化物を再生装置へ移送する必要はなく、容器に収容したままで、再生剤を接触させることにより再生するようにしてもよい。
第1ユニット50で生成される使用済みの層状複水酸化物を第2ユニット60で再生した再生物を用いるだけでなく、未使用の層状複水酸化物や、外部で生成された再生物を適宜補給するようにしてもよい。
内径16mmのガラス製の反応管に0.1gのOH型Mg-Al層状複水酸化物を充填し、窒素ガスを反応管の上流から流通し、各反応管を管状電気炉で流通するガス温度が170℃になるように調整した。
塩化水素を1,000ppmになるように窒素を流通しながら、マスフローコントローラーで各ガスの流量を調整し、反応管における空塔速度が1.0m/minになるように反応管に上記の混合ガスを通過させた。
試験開始後の反応管の出口の流通ガス中の塩化水素濃度をFT-IR式ガス分析計によって連続測定し、破過曲線を作成した。
実施例1で用いたOH型Mg-Al層状複水酸化物の化学式は以下のとおりである(分子量:118.86)。
[Mg0.67Al0.33(OH)2](OH-)0.33・3H2O・・・式(1)
上記OH型Mg-Al層状複水酸化物は、以下に示す手順によって合成した。
硝酸マグネシウム六水和物及び硝酸アルミニウム九水和物を用いて、マグネシウム濃度0.33mol/L、アルミニウム濃度0.17mol/Lの混合水溶液(マグネシウム/アルミニウム=2/1(モル比))を調製した。
この混合溶液500mLを、濃度0.1mol/Lの炭酸ナトリウム水溶液500mLに、30℃で撹拌しながら滴下した。このとき、濃度1.25mol/Lの水酸化ナトリウム水溶液の滴下により、pHを10.5に保持した。
滴下終了後、30℃で1時間撹拌した。その後、沈殿物をろ過し、繰り返し純水で洗浄した後、40℃で40時間減圧乾燥し、CO3型Mg-Al層状複水酸化物を得た。
得られたCO3型Mg-Al層状複水酸化物を500℃で2時間仮焼した後、濃度0.2mol/Lの水酸化ナトリウム水溶液に、窒素ガス気流下で投入し、30℃で3時間撹拌した。その後、沈殿物をろ過し、繰り返し純水で洗浄した後、40℃で減圧乾燥し、OH型Mg-Al層状複水酸化物を得た。
Mg0.67Al0.33O1.17+0.33OH-+1.17H2O
→ Mg0.67Al0.33(OH)2(OH-)0.33+xOH-・・・式(2)
上記の理論式(2)に基づいて反応が進むことから、上記化学式(1)であると同定した。
OH型Mg-Al層状複水酸化物に代えて、CO3型Mg-Al層状複水酸化物を用いた以外は実施例1と同様にして測定を行い、破過曲線を作成した。
比較例1で用いたCO3型Mg-Al層状複水酸化物の化学式は以下のとおりである(分子量:123.2)。
[Mg0.67Al0.33(OH)2](CO3 2-)0.17・3H2O・・・式(3)
上記CO3型Mg-Al層状複水酸化物は、以下に示す手順によって合成した。
硝酸マグネシウム六水和物及び硝酸アルミニウム九水和物を用いて、マグネシウム濃度0.33mol/L、アルミニウム濃度0.17mol/Lの混合水溶液(マグネシウム/アルミニウム=2/1(モル比))を調製した。
この混合溶液を、濃度0.1mol/Lの炭酸ナトリウム水溶液に、30℃で撹拌しながら滴下した。このとき、濃度1.25mol/Lの水酸化ナトリウム水溶液の滴下により、pHを10.5に保持した。
滴下終了後、30℃で1時間撹拌した。その後、沈殿物をろ過し、純水で繰り返し洗浄した後、40℃で40時間減圧乾燥し、CO3型Mg-Al層状複水酸化物を得た。
そして、上記合成物はCO3型Mg-Al層状複水酸化物の理論式に基づいて反応が進むことから、上記化学式(3)であると同定した。
また、下記の反応式(4)と、上記式(1)及び式(3)の層状複水酸化物の分子量とに基づいて、実施例1及び比較例1において供試した各々の塩化水素の飽和吸着量を求めると、実施例1のOH型Mg-Al層状複水酸化物では0.101g/gであり、比較例1のCO3型Mg-Al層状複水酸化物では0.098g/gとなり、両者はほぼ同等の値である。このことから、吸着塔の破過時間を一定に設計した場合、OH型Mg-Al層状複水型酸化物を用いた実施例1の方が、CO3型Mg-Al層状複水酸化物を用いた比較例1よりも少ない充填量で、酸性排ガスの処理を行うことが可能であることが判る。
[M1-xM’x(OH)2]An- x/n・mH2O+xHCl
→ [M1-xM’x(OH)2]Clx・mH2O+x/nAn-・・・式(4)
[M0.67Al0.33(OH)2](Cl-)0.33・3H2O・・・式(5)
そして、上記化学式(5)の化合物を、水酸化ナトリウムを再生剤として上記化学式(1)の層状複水酸化物に、また、炭酸ナトリウムを再生剤として上記化学式(3)の層状複水酸化物に、それぞれ再生する場合の再生反応式は下記の式(6)、式(7)で表される。
[M0.67Al0.33(OH)2](Cl-)0.33・3H2O+0.33NaOH
→ [Mg0.67Al0.33(OH)2](OH-)0.33・3H2O+0.33NaCl
・・・式(6)
[M0.67Al0.33(OH)2](Cl-)0.33・3H2O+0.17Na2CO3
→ [Mg0.67Al0.33(OH)2](CO3 2-)0.33・3H2O+0.33NaCl
・・・式(7)
上記式(6)、式(7)、各再生剤の分子量(NaOH:40、Na2CO3:106)、及び、上記式(5)の化合物の分子量(124.91)に基づいて、各再生剤の当量を算出すると以下のようになり、OH型Mg-Al層状複水型酸化物を用いた実施例1の方が少ない当量の再生剤で再生可能であることが判る。なお、「LDH」は「層状複水酸化物」を意味する。
・NaOH/LDH:0.33×40/124.91≒0.10567
・Na2CO3/LDH:0.17×106/124.91≒0.14426
12:ボイラ
13:ガス冷却装置
14:集塵機
15:誘因通風機
16:煙突
21~23、25、26:配管(煙道)
24:第1の配管
31:層状複水酸化物収容容器
40:再生装置
41:第2の配管
50:第1ユニット
60:第2ユニット
80:酸性排ガスの処理設備
100:焼却施設
Claims (10)
- 酸性排ガスの処理方法であって、OH型Mg-Al層状複水酸化物を用いて、酸性排ガス中の酸性ガスを処理する第1の工程を有する、酸性排ガスの処理方法。
- 前記第1の工程で使用するOH型Mg-Al層状複水酸化物は、破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンに交換して得られる再生物を含む、請求項1に記載の酸性排ガスの処理方法。
- 破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンにイオン交換して、OH型Mg-Al層状複水酸化物の再生物を生成する第2の工程を更に有し、
前記第1の工程では、前記第2の工程で生成した前記再生物の少なくとも一部を使用する、請求項1又は2に記載の酸性排ガスの処理方法。 - 破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンにイオン交換して、OH型Mg-Al層状複水酸化物の再生物を生成する第2の工程を更に有し、
前記第2の工程においては、前記第1の工程で酸性排ガス処理に供したOH型Mg-Al層状複水酸化物を用いて前記再生物を生成する、請求項1又は2に記載の酸性排ガスの処理方法。 - 破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンにイオン交換して、OH型Mg-Al層状複水酸化物の再生物を生成する第2の工程を更に有し、
前記第1の工程及び前記第2の工程を1サイクルとして、当該サイクルを繰り返し実行し、
2回目以降のいずれかのサイクルの前記第1の工程で用いられるOH型Mg-Al層状複水酸化物の少なくとも一部として、当該サイクル以前のサイクルの第2工程で再生した再生物を用いる、請求項1又は2に記載の酸性排ガスの処理方法。 - 請求項1~5のいずれか1項に記載の酸性排ガスの処理方法を行う手段を有する、酸性排ガスの処理設備。
- 前記第1の工程で用いるOH型Mg-Al層状複水酸化物を収容する容器と、発生源から発生する酸性排ガスを前記容器に導くための第1の配管とを含む第1ユニットを有する、請求項6に記載の酸性排ガスの処理設備。
- 破過したOH型Mg-Al層状複水酸化物の層間アニオンを水酸化物イオンに交換して再生物を生成する再生装置と、前記再生装置から前記再生物を前記第1ユニットに導くための第2の配管とを含む第2ユニットを更に有する、請求項7に記載の酸性排ガスの処理設備。
- 前記第2の配管は、前記第1ユニットから酸性排ガス処理に供したOH型Mg-Al層状複水酸化物を前記再生装置に導くとともに、前記再生装置から前記再生物を前記第1ユニットに導く、請求項8に記載の酸性排ガスの処理設備。
- 焼却炉と、請求項6~9のいずれか1項に記載の酸性排ガスの処理設備と、を有する焼却施設。
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US5882622A (en) * | 1995-06-07 | 1999-03-16 | Aluminum Company Of America | Carbon dixide adsorption of synthetic meixnerite |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Non-Patent Citations (3)
Title |
---|
EIJI ISHIZAKI: "Ph. D. thesis", September 2016, GRADUATE SCHOOL OF SCI. AND ENG., IBARAKI UNIV., article "Research of Calculator Simulation of Adsorption Dynamics in Adsorption Tower", pages: 28,29 |
JOURNAL OF MATERIALS SCIENCE, vol. 42, 2007, pages 9210 - 9215 |
WILLIAM TONGAMP ; QIWU ZHANG ; FUMIO SAITO: "Preparation of meixnerite (Mg–Al–OH) type layered double hydroxide by a mechanochemical route", JOURNAL OF MATERIALS SCIENCE, KLUWER ACADEMIC PUBLISHERS, BO, vol. 42, no. 22, 27 July 2007 (2007-07-27), Bo , pages 9210 - 9215, XP019528942, ISSN: 1573-4803, DOI: 10.1007/s10853-007-1866-5 * |
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