JP5286480B2 - Method for producing particulate Ca (OH) 2 and gas absorption method or gas recovery method using the same - Google Patents
Method for producing particulate Ca (OH) 2 and gas absorption method or gas recovery method using the same Download PDFInfo
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- JP5286480B2 JP5286480B2 JP2007226919A JP2007226919A JP5286480B2 JP 5286480 B2 JP5286480 B2 JP 5286480B2 JP 2007226919 A JP2007226919 A JP 2007226919A JP 2007226919 A JP2007226919 A JP 2007226919A JP 5286480 B2 JP5286480 B2 JP 5286480B2
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- 238000000034 method Methods 0.000 title claims description 26
- 238000010521 absorption reaction Methods 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000011084 recovery Methods 0.000 title claims description 8
- 239000011575 calcium Substances 0.000 claims description 68
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 62
- 239000000292 calcium oxide Substances 0.000 claims description 29
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 15
- 235000019738 Limestone Nutrition 0.000 claims description 13
- 239000006028 limestone Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 244000299461 Theobroma cacao Species 0.000 claims description 6
- 235000005764 Theobroma cacao ssp. cacao Nutrition 0.000 claims description 6
- 235000005767 Theobroma cacao ssp. sphaerocarpum Nutrition 0.000 claims description 6
- 235000001046 cacaotero Nutrition 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 38
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000000920 calcium hydroxide Substances 0.000 description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- -1 CO 2 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は、粒子状のCa(OH)2の製造方法及びそれを用いたガス吸収方法又は回収方法に関し、より詳しくは、一定強度を持つ粒子状のCa(OH)2の製造方法、及びそれを利用した比表面積が大きい粒子状CaOの製造方法、これらを用いたガス吸収方法並びにガス回収方法に関するものである。 The present invention relates to a method for producing particulate Ca (OH) 2 and a gas absorption method or recovery method using the same, and more particularly, a method for producing particulate Ca (OH) 2 having a certain strength, and the same. The present invention relates to a method for producing particulate CaO having a large specific surface area utilizing the above, a gas absorption method using these, and a gas recovery method.
従来、移動層や固定層などにおいて、粒子状のCa(OH)2を反応させる際に、一定強度を持たない粒子状のCa(OH)2は、反応気流により粒子が破壊されて粉末化されてしまうため、気流と共に反応系外に持ち出されてしまうため、反応効率が著しく低下する。 Conventionally, in such moving bed and fixed bed, in the reaction of particulate Ca (OH) 2, particulate Ca (OH) 2 without a constant intensity, the particles are broken is powdered by reaction stream Therefore, it is taken out of the reaction system together with the air flow, and the reaction efficiency is significantly reduced.
とくに、粒子状の酸化カルシウム（CaO）を用いて、これを水ないし水蒸気と反応させて粒子状のCa(OH)2として利用する反応系においては、一定強度を持たない粒子状のCa(OH)2が生成してしまうため、流速が早い反応気流を用いることが出来なかった。
本発明者が開発したHyPr-RING法（特許文献１−７参照）は、粒子状の酸化カルシウム（CaO）を用いて、水素製造と共にカルシウムベース吸収剤（CaO）を使ってガス化炉内でCO2を吸収分離している。
In particular, in a reaction system that uses particulate calcium oxide (CaO) and reacts with water or water vapor as particulate Ca (OH) 2 , particulate Ca (OH) that does not have a constant strength. ) 2 was generated, so it was not possible to use a reaction air flow with a high flow rate.
The HyPr-RING method developed by the present inventor (see Patent Documents 1-7) uses particulate calcium oxide (CaO) in a gasifier using a calcium-based absorbent (CaO) together with hydrogen production. CO 2 is absorbed and separated.
しかし、カ焼と共に酸化カルシウム（CaO）の焼結が進み、酸化カルシウム（CaO）のガス吸収活性が低下してしまうため、従来法では活性が低下した粒子状の酸化カルシウム（CaO）に水や水蒸気を吹き付け、水酸化カルシウムCa(OH)2を生成させて活性を回復する方法が考えられていが、酸化カルシウム（CaO）を粒子状としたものを用いても、生成した水酸化カルシウムCa(OH)2が粉末化するため、気流により排出されてしまって、移動層や固定層などにおいて吸収剤として使用できなくなる問題があった。 However, the sintering of calcium oxide (CaO) proceeds with calcination, and the gas absorption activity of calcium oxide (CaO) decreases, so water and water are added to particulate calcium oxide (CaO), which has decreased activity in the conventional method. Although the method of spraying water vapor and generating calcium hydroxide Ca (OH) 2 to recover the activity has been considered, even if calcium oxide (CaO) in the form of particles is used, the generated calcium hydroxide Ca ( Since OH) 2 is pulverized, it is discharged by an air stream and cannot be used as an absorbent in a moving bed or a fixed bed.
さらに、本発明者は、CaCO3から活性の高い酸化カルシウム（CaO）を製造しつつCO2を回収することができるカ焼方法についても既に提案しているところである（特許文献８参照）。 Furthermore, the present inventor has already proposed a calcining method capable of recovering CO 2 while producing highly active calcium oxide (CaO) from CaCO 3 (see Patent Document 8).
本発明者は、上記の問題点を解決すべく、粒子状の酸化カルシウム（CaO）と水又は水蒸気とを反応させ、水酸化カルシウムCa(OH)2を生成させた際に、一定強度をもつ粒子状の水酸化カルシウムCa(OH)2とする水酸化カルシウムCa(OH)2の製造方法及びそれを利用した比表面積が大きい粒子状CaOの製造方法、これらを用いたガス吸収方法又は回収方法を提供する。 In order to solve the above-mentioned problems, the present inventor has a certain strength when calcium hydroxide Ca (OH) 2 is generated by reacting particulate calcium oxide (CaO) with water or water vapor. method for producing a particulate calcium hydroxide Ca (OH) 2 to calcium hydroxide Ca (OH) 2 preparation and use the large specific surface area particulate CaO it, gas absorption method or recovering method using these I will provide a.
本発明者は、鋭意研究を続けた結果、酸化カルシウム（CaO）と水又は水蒸気とを１気圧以上２００〜７００℃で反応させることにより、一定強度をもつ粒子状の水酸化カルシウムCa(OH)2とすることができることを見出し、本発明を完成させるに至った。すなわち、本発明は、石灰石若しくは炭酸カルシウム（CaCaO ３ ）をカ焼して得られた粒子状酸化カルシウム（CaO）であって、前記粒子状酸化カルシウム（CaO）の粒子径が０．２〜０．８ｍｍである粒子状酸化カルシウム（CaO）を、水と反応させ、
ＣａＯ＋Ｈ２Ｏ→Ｃａ（ＯＨ）2 （１）
で表される反応をさせるに際して、１気圧以上で６５０〜７００℃の水蒸気条件で反応（１）を進行させることにより、圧縮破壊強度が２５ｋｇ/cm 2 以上で粒子状を保持したままのCa(OH)2を生成させ、次いで、８５０℃〜９００℃で熱分解することを特徴とする比表面積が大きい粒子状CaOの製造方法である。
また、本発明は、石灰石若しくは炭酸カルシウム（CaCaO ３ ）をカ焼して得られた粒子状酸化カルシウム（CaO）であって、前記粒子状酸化カルシウム（CaO）の粒子径が０．２０〜０．８ｍｍである粒子状酸化カルシウム（CaO）を、水と反応させ、
ＣａＯ＋Ｈ２Ｏ→Ｃａ（ＯＨ）2 （１）
で表される反応をさせるに際して、１気圧以上で６５０〜７００℃の条件で反応（１）を進行させることにより、圧縮破壊強度が２５ｋｇ/cm 2 以上で粒子状を保持したままのCa(OH)2を生成させ、次いで、それを８５０℃〜９００℃で熱分解して出来たCaOと、HCL,H2S,SO2,CO2,ハロゲンから選ばれる有害ガス(R)を、９００℃以下の温度で反応させ、Ca(R)を生成させるガス吸収方法である。
さらに、本発明は上記のガス吸収方法で生成したCa(R)を、温度100℃〜800℃、１気圧〜１００気圧の水蒸気で処理し、再びCa(OH)2に再生し、得られたCa(OH)2を有害ガス吸収剤として再利用しながら、生成した高濃度の有害ガス（R）を回収するガス回収方法である。
As a result of continual research, the present inventor has reacted calcium oxide (CaO) with water or water vapor at 1 atm or more at 200 to 700 ° C. to thereby form particulate calcium hydroxide Ca (OH) having a certain strength. As a result, the present invention has been completed. That is, the present invention is particulate calcium oxide (CaO) obtained by calcining limestone or calcium carbonate (CaCaO 3 ), and the particle diameter of the particulate calcium oxide (CaO) is 0.2 to 0. .8 mm of particulate calcium oxide (CaO) is reacted with water,
CaO + H 2 O → Ca (OH) 2 (1)
When the reaction represented by the formula (1) is performed, the reaction (1) is allowed to proceed under a water vapor condition of 650 to 700 ° C. at 1 atm or higher, so that the compressive fracture strength is 25 kg / cm 2 or more while maintaining the particulate form of Ca ( This is a method for producing particulate CaO having a large specific surface area, characterized by producing OH) 2 and then thermally decomposing at 850 ° C to 900 ° C.
The present invention also relates to particulate calcium oxide (CaO) obtained by calcining limestone or calcium carbonate (CaCaO 3 ), wherein the particle diameter of the particulate calcium oxide (CaO) is 0.20 to 0. .8 mm of particulate calcium oxide (CaO) is reacted with water,
CaO + H 2 O → Ca (OH) 2 (1)
When the reaction represented by the formula (1) is carried out under the conditions of 650 to 700 ° C. at 1 atm or more, Ca (OH) with the compressive fracture strength of 25 kg / cm 2 or more and maintaining the particulate form is maintained. ) 2 and then pyrolyzing it at 850 ° C. to 900 ° C. and a harmful gas (R) selected from HCL, H 2 S, SO 2 , CO 2 and halogen at 900 ° C. It is a gas absorption method in which Ca (R) is generated by reacting at the following temperatures.
Furthermore, the present invention was obtained by treating Ca (R) produced by the above gas absorption method with water vapor at a temperature of 100 ° C. to 800 ° C. and 1 atm to 100 atm, and regenerating Ca (OH) 2 again. This is a gas recovery method that recovers high-concentration harmful gas (R) while reusing Ca (OH) 2 as a harmful gas absorbent.
本発明の粒子状のCa(OH)2の製造方法は、安価な石灰石からも作ることができ、一定強度をもつ粒子状のCa(OH)2を造ることが出来る。また、粒子状のCa(OH)2として移動層や固定層吸収塔に有効に使用することができる。さらに、本発明の粒子状のCa(OH)2を熱分解することを特徴とする比表面積が大きい粒子状CaOを作ることができ、これらの物質は反応性が高く、有毒ガスのガス吸収方法又はガス回収方法に用いることができる。 The method for producing particulate Ca (OH) 2 of the present invention can be produced from inexpensive limestone, and particulate Ca (OH) 2 having a certain strength can be produced. Further, it can be effectively used as a particulate Ca (OH) 2 in a moving bed or a fixed bed absorption tower. Furthermore, it is possible to produce particulate CaO having a large specific surface area, characterized by thermally decomposing particulate Ca (OH) 2 of the present invention, and these substances are highly reactive and a gas absorption method for toxic gas Or it can use for a gas recovery method.
本発明において、用いることが出来る粒子状酸化カルシウム（CaO）としては、石灰石若
しくは炭酸カルシウム（CaCO3）をカ焼したものや、市販の生石灰である。粒子状酸化カ
ルシウム（CaO）の粒子径は、０．２〜０．８ｍｍ程度のもの、好ましくは０．３〜０．
６ｍｍのものを用いることが出来る。
粒子径は０．２ｍｍ未満では、移動層や固定層などにおいて、気流と共に反応系外に持ち
出されてしまうため好ましくなく、０．８ｍｍを超えるものは用途が少ない。
また、反応は、１気圧以上で６５０℃〜７００℃で行う。
本発明において、原料として用いる粒子状酸化カルシウム（CaO）の原料としての炭酸カ
ルシウム（CaCO3）は、どのような炭酸カルシウムでも良いが、HyPr-RING法の使用済み生成物としての吸収剤(CaCO3炭酸塩）が好適に用いられる。
In the present invention, particulate calcium oxide (CaO) that can be used is a calcined limestone or calcium carbonate (CaCO3) or commercially available quicklime. The particle diameter of particulate calcium oxide (CaO) is about 0.2 to 0.8 mm, preferably 0.3 to 0.00 mm.
6 mm can be used.
If the particle diameter is less than 0.2 mm, it is not preferable because it is taken out of the reaction system together with the air current in the moving layer, the fixed layer, etc., and those exceeding 0.8 mm have few applications.
Moreover, reaction is performed at 650 degreeC-700 degreeC above 1 atmosphere.
In the present invention, calcium carbonate (CaCO 3 ) as a raw material of particulate calcium oxide (CaO) used as a raw material may be any calcium carbonate, but an absorbent (CaCO as a used product of the HyPr-RING method) 3 carbonate) is preferably used.
得られる粒子状水酸化カルシウム（Ca(OH)2）は、圧縮破壊強度が、一定強度２５ｋｇ/cm 2 以上であれば、安定的に粒子形状を維持することが出来る。本発明では、圧縮破壊強度が５０ｋｇ/cm2以上のものも作ることも出来る。得られた粒子状水酸化カルシウム（Ca(OH)2）は、図１に示すように炭酸ガス吸収剤、高温脱硫剤、脱塩化水素剤、脱水剤、ヒートポンプ熱媒体、充填材など多くの用途に用いることが出来る。さらに、高温脱硫剤として用いる具体的な例として、図２に示す排ガス処理システムを示すことが出来る。
The obtained particulate calcium hydroxide (Ca (OH) 2 ) can stably maintain the particle shape if the compressive fracture strength is a constant strength of 25 kg / cm 2 or more. In the present invention, one having a compressive fracture strength of 50 kg / cm 2 or more can also be produced. The obtained particulate calcium hydroxide (Ca (OH) 2 ) has many uses such as carbon dioxide absorbent, high-temperature desulfurizing agent, dehydrochlorinating agent, dehydrating agent, heat pump heat medium, filler as shown in FIG. Can be used. Furthermore, an exhaust gas treatment system shown in FIG. 2 can be shown as a specific example used as a high-temperature desulfurization agent.
本件発明において、比表面積が大きいとは、気体吸着によるＢＥＴ式表面積測定法で、２０．０m2/g〜４０．０m2/gの値を示すものをいう。
気体吸着によるＢＥＴ式表面積測定法は、業界周知である。
また、原料の粒子状CaOの比表面積は、１２．０m2/g以下であっても良く、生成した粒子状CaOの比表面積は、２０．０m2/g〜４０．０m2/gとなる。
さらに、本発明における一定強度をもつ粒子状の水酸化カルシウムCa(OH)2の熱分解の温度は、通常４００℃〜１０００℃であり、８５０℃〜９００℃が好ましい。４００℃未満では、反応が遅く、１０００℃以上ではエネルギー効率が悪い。
本発明において、原料の粒子状CaOは、石灰石若しくは炭酸カルシウム（CaCO3）をカ焼することにより得られるが、カ焼は、どのような条件でも良く、とくに、水蒸気分圧５０〜8０％、炭酸ガス分圧２０〜５０％（水蒸気と炭酸ガスによる全圧0.05−0.15Mpaの条件下）の雰囲気下、温度７５０〜１０００℃以下の条件でカ焼を行うことが好ましい。
さらに、本発明において、粒子状Ca(OH)2若しくはそれを熱分解して出来たCaOと反応させて、ガス吸収を行う有害ガス(R)としては、代表的には、HCL, H2S, SO2, CO2, ハロゲン等を挙げることができる。ガス吸収反応は、エネルギー効率を考えると９００℃以下で行うことが望ましい。
これらの有害ガス(R)は、カルシウム（Ca）と化合するが、水蒸気とくに、100℃〜800℃、１気圧〜100気圧の水蒸気で処理すると、
Ca(OH)2と元のガス体に分離させることができ、再生されたCa(OH)2は、再利用することができる。また、水蒸気温度は１００℃未満では反応が遅くて効率が悪く、８００℃以上ではエネルギー効率が悪くなる。水蒸気圧力は、1気圧未満では反応が遅く、１００気圧以上では装置の作成に手間が掛かりすぎる。
In the present invention, the specific surface area is large, the BET equation surface area measurement method by gas adsorption, refers to indicating the value of 20.0m 2 /g~40.0m 2 / g.
The BET surface area measurement method by gas adsorption is well known in the industry.
The specific surface area of the particulate CaO in the raw material may be less than or equal 12.0m 2 / g, a specific surface area of the produced particulate CaO is a 20.0m 2 /g~40.0m 2 / g .
Furthermore, the thermal decomposition temperature of the particulate calcium hydroxide Ca (OH) 2 having a constant strength in the present invention is usually 400 ° C. to 1000 ° C., preferably 850 ° C. to 900 ° C. If it is less than 400 degreeC, reaction will be slow, and if it is 1000 degreeC or more, energy efficiency is bad.
In the present invention, the raw material granular CaO is obtained by calcining limestone or calcium carbonate (CaCO 3 ), and calcining may be performed under any conditions, in particular, a water vapor partial pressure of 50 to 80%, It is preferable to perform calcination under a temperature of 750 to 1000 ° C. under an atmosphere of carbon dioxide partial pressure of 20 to 50% (under conditions of a total pressure of 0.05 to 0.15 MPa by steam and carbon dioxide).
Furthermore, in the present invention, the harmful gas (R) that absorbs gas by reacting with particulate Ca (OH) 2 or CaO obtained by thermally decomposing it is typically HCL, H 2 S. , SO 2 , CO 2 , halogen and the like. The gas absorption reaction is desirably performed at 900 ° C. or lower in view of energy efficiency.
These harmful gases (R) combine with calcium (Ca), but when treated with water vapor, particularly 100 ° C. to 800 ° C., 1 atm to 100 atm,
Ca (OH) 2 can be separated from the original gas body, and the regenerated Ca (OH) 2 can be reused. Further, when the water vapor temperature is less than 100 ° C, the reaction is slow and the efficiency is poor, and when it is 800 ° C or more, the energy efficiency is deteriorated. If the water vapor pressure is less than 1 atm, the reaction is slow, and if it exceeds 100 atm, it takes too much time to create the apparatus.
本発明の実施の形態は以下のとおりである。
（イ）石灰石若しくは炭酸カルシウム（CaCaO ３ ）をカ焼して得られた粒子状酸化カルシウム（CaO）であって、前記粒子状酸化カルシウム（CaO）の粒子径が０．２〜０．８ｍｍである粒子状酸化カルシウム（CaO）を、水と反応させ、
ＣａＯ＋Ｈ２Ｏ→Ｃａ（ＯＨ）2 （１）
で表される反応をさせるに際して、１気圧以上で６５０〜７００℃の水蒸気条件で反応（１）を進行させることにより、圧縮破壊強度が２５ｋｇ/cm 2 以上で粒子状を保持したままのCa(OH)2を生成させ、次いで、８５０℃〜９００℃で熱分解することを特徴とする比表面積が大きい粒子状CaOの製造方法。
（ロ）石灰石若しくは炭酸カルシウム（CaCaO ３ ）をカ焼して得られた粒子状酸化カルシウム（CaO）であって、前記粒子状酸化カルシウム（CaO）の粒子径が０．２０〜０．８ｍｍである粒子状酸化カルシウム（CaO）を、水と反応させ、
ＣａＯ＋Ｈ２Ｏ→Ｃａ（ＯＨ）2 （１）
で表される反応をさせるに際して、１気圧以上で６５０〜７００℃の条件で反応（１）を進行させることにより、圧縮破壊強度が２５ｋｇ/cm 2 以上で粒子状を保持したままのCa(OH)2を生成させ、次いで、それを８５０℃〜９００℃で熱分解して出来たCaOと、HCL,H2S,SO2,CO2,ハロゲンから選ばれる有害ガス(R)を、９００℃以下の温度で反応させ、Ca(R)を生成させるガス吸収方法。
（ハ）上記に係るガス吸収方法で生成したCa(R)を、温度100℃〜800℃、１気圧〜１００気圧の水蒸気で処理し、再びCa(OH)2に再生し、得られたCa(OH)2を有害ガス吸収剤として再利用しながら、生成した高濃度の有害ガス（R）を回収するガス回収方法。
次に本発明の具体例を示す。
Embodiments of the present invention are as follows.
(I) It is particulate calcium oxide (CaO) obtained by calcining limestone or calcium carbonate (CaCaO 3 ), and the particle diameter of the particulate calcium oxide (CaO) is 0.2 to 0.8 mm. Some particulate calcium oxide (CaO) reacts with water,
CaO + H 2 O → Ca (OH) 2 (1)
When the reaction represented by the formula (1) is performed, the reaction (1) is allowed to proceed under a water vapor condition of 650 to 700 ° C. at 1 atm or higher, so that the compressive fracture strength is 25 kg / cm 2 or more while maintaining the particulate form of Ca ( OH) 2 is produced, and then pyrolyzed at 850 ° C. to 900 ° C. A method for producing particulate CaO having a large specific surface area.
(B) Particulate calcium oxide (CaO) obtained by calcining limestone or calcium carbonate (CaCaO 3 ), wherein the particle diameter of the particulate calcium oxide (CaO) is 0.20 to 0.8 mm. Some particulate calcium oxide (CaO) reacts with water,
CaO + H 2 O → Ca (OH) 2 (1)
When the reaction represented by the formula (1) is carried out under the conditions of 650 to 700 ° C. at 1 atm or more, Ca (OH) with the compressive fracture strength of 25 kg / cm 2 or more and maintaining the particulate form is maintained. ) 2 and then pyrolyzing it at 850 ° C. to 900 ° C. and a harmful gas (R) selected from HCL, H 2 S, SO 2 , CO 2 and halogen at 900 ° C. A gas absorption method in which Ca (R) is produced by reacting at the following temperatures.
(C) Ca (R) produced by the gas absorption method according to the above is treated with water vapor at a temperature of 100 ° C. to 800 ° C. and 1 atm to 100 atm, regenerated again to Ca (OH) 2 , and obtained Ca A gas recovery method that recovers high concentration of harmful gas (R) while reusing (OH) 2 as a harmful gas absorbent.
Next, specific examples of the present invention will be shown.
石灰石を、通常の方法すなわち、窒素／炭酸ガス＝６／４の雰囲気で９２０℃の温度でカ焼することにより得られた低活性粒子状酸化カルシウム（CaO）（ＢＥＴ１０．２ｍ２／ｇ）を用いて、３．０Ｍｐａで650℃の水蒸気条件で反応させ、粒子状のCa(OH)2（ＢＥＴ５．３ｍ２／ｇ）を生成させた。得られた粒子状のCa(OH)2（ＢＥＴ５．３ｍ２／ｇ）の粒度分布及び強度を表１に示す。 Low activity particulate calcium oxide (CaO) (BET 10.2 m 2 / g) obtained by calcining limestone in a usual manner, that is, by calcining at a temperature of 920 ° C. in an atmosphere of nitrogen / carbon dioxide gas = 6/4. It was used and reacted under steam conditions of 3.0 Mpa and 650 ° C. to produce particulate Ca (OH) 2 (BET 5.3 m 2 / g). Table 1 shows the particle size distribution and strength of the obtained particulate Ca (OH) 2 (BET 5.3 m 2 / g).
石灰石を、通常の方法すなわち、窒素／炭酸ガス＝６／４の雰囲気で９２０℃の温度でカ焼することにより得られた粒子状CaO（ＢＥＴ１０．２ｍ２／ｇ）を用いて、３．０Ｍｐａで650℃の水蒸気条件で反応させ、粒子状のCa(OH)2（ＢＥＴ５．３ｍ２／ｇ）を生成させた。次いで生成したCa(OH)2を９００℃１気圧の条件で熱分解したところ、ＢＥＴ３０．４ｍ２／ｇの粒子状のCaOを得ることが出来た。
得られた粒子状のCa(OH)2（ＢＥＴ５．３ｍ２／ｇ）とCaO（ＢＥＴ３０．４ｍ２／ｇ）の粒度分布及び強度を表２に示す。
Using particulate CaO (BET 10.2 m 2 / g) obtained by calcining limestone in a usual manner, that is, at a temperature of 920 ° C. in an atmosphere of nitrogen / carbon dioxide gas = 6/4, 3.0 Mpa The reaction was carried out under steam conditions at 650 ° C. to produce particulate Ca (OH) 2 (BET 5.3 m 2 / g). Next, when the produced Ca (OH) 2 was pyrolyzed at 900 ° C. and 1 atmosphere, particulate CaO having a BET of 30.4 m 2 / g could be obtained.
Table 2 shows the particle size distribution and strength of the obtained particulate Ca (OH) 2 (BET 5.3 m 2 / g) and CaO (BET 30.4 m 2 / g).
また、実施例１で得られた粒子状のCa(OH)2（ＢＥＴ５．３ｍ２／ｇ）とCaO（ＢＥＴ３０．４ｍ２／ｇ）の顕微鏡写真を図３に示す。
さらに、通常の方法すなわち、粉末状の石灰石を、窒素／炭酸ガス＝６／４の雰囲気で９２０℃の温度でカ焼することにより得られた通常の粒子状酸化カルシウム（CaO）（ＢＥＴ１０．２ｍ２／ｇ）を作成したCaO、実施例１により得られたCa(OH)2及び実施例２により得られたCaOの比表面積（ＢＥＴ ｍ２／ｇ）を表３に示す。
Further, FIG. 3 shows micrographs of the particulate Ca (OH) 2 (BET 5.3 m 2 / g) and CaO (BET 30.4 m 2 / g) obtained in Example 1.
Furthermore, normal particulate calcium oxide (CaO) (BET10.2 m obtained by calcining powdery limestone at a temperature of 920 ° C. in an atmosphere of nitrogen / carbon dioxide gas = 6/4. 2 / g) was created CaO, specific surface area of CaO obtained by Ca (OH) 2 and example 2 obtained in example 1 (
（粒子状Ca(OH)2によるガス吸収の実施例）
Ca(OH)2による高温H2S吸収工程は、以下の反応で高温H2Sを吸収する。
Ca(OH)2→CaO+H2O; 昇温中
CaO+H2S→CaS+H2O; 高温H2S吸収
1gの粒子状Ca(OH)2を高温高圧固定層吸収塔にセットして、昇温昇圧する。Ca(OH)2は昇温中に粒子状CaOに分解する。800℃、15気圧で400ppmH2SとN2からなる混合ガス2.5L/minを流し、吸収実験を開始する。同時に出口ガス中のH2Sの濃度を測定する。図４には出口ガス測定結果を示す。100分まで供給ガス中のH2Sの殆どが粒子状CaOに吸収されていたことが分かる。
(Example of gas absorption by particulate Ca (OH) 2 )
Ca (OH) 2 at a high temperature H 2 S absorption step absorbs high temperature H 2 S in the following reaction.
Ca (OH) 2 → CaO + H 2 O; heating
CaO + H 2 S → CaS + H 2 O; high temperature H 2 S absorption
1 g of particulate Ca (OH) 2 is set in a high-temperature, high-pressure fixed bed absorption tower, and the temperature is increased. Ca (OH) 2 decomposes into particulate CaO during heating. Absorption experiment is started by flowing 2.5L / min of mixed gas consisting of 400ppmH 2 S and N 2 at 800 ° C and 15 atm. At the same time, the concentration of H 2 S in the outlet gas is measured. FIG. 4 shows the outlet gas measurement results. It can be seen that most of the H 2 S in the feed gas was absorbed by the particulate CaO until 100 minutes.
（生成CaSの再生工程）
実施例３で生成したCaSは、以下の反応により再生することができる。
CaS+高温高圧蒸気→Ca(OH)2+ H2S
まず、CaSを高温高圧装置にセットし、昇温昇圧する。400℃及び30気圧に固定し、高温高圧水蒸気を導入してCaSの再生を開始する。同時に出口ガスを測定し、生成されたH2Sの量からCaSからCa(OH)2への転換率を算出する。図５にはCaSからCa(OH)2への再生試験の例を示す。
図から、120分で、転換率（回収率）が５０％以上になることが判る。
(Regeneration process of generated CaS)
The CaS produced in Example 3 can be regenerated by the following reaction.
CaS + high temperature and high pressure steam → Ca (OH) 2 + H 2 S
First, CaS is set in a high-temperature and high-pressure device, and the temperature is raised and raised. The temperature is fixed at 400 ° C. and 30 atmospheres, and high temperature and high pressure steam is introduced to start regeneration of CaS. At the same time, the outlet gas is measured, and the conversion rate from CaS to Ca (OH) 2 is calculated from the amount of H 2 S produced. FIG. 5 shows an example of a regeneration test from CaS to Ca (OH) 2 .
From the figure, it can be seen that the conversion rate (recovery rate) is 50% or more in 120 minutes.
本発明の粒子状のCa(OH)2の製造方法は、安価な石灰石からも作ることができ、一定強度をもつ粒子状のCa(OH)2を造ることが出来る。粒子状のCa(OH)2として移動層や固定層吸収塔に有効に使用することができるばかりか、本発明の粒子状のCa(OH)2を熱分解することで比表面積が大きい粒子状CaOを作ることができる。
さらにこれらの物質は反応性が高く、有毒ガスの吸収方法又は回収方法に用いることができるため、多くに用途があり、産業上利用価値の高いものである。
The method for producing particulate Ca (OH) 2 of the present invention can be produced from inexpensive limestone, and particulate Ca (OH) 2 having a certain strength can be produced. Not only can be effectively used in the transfer layer and the fixed layer absorber column as particulate Ca (OH) 2, particulate Ca (OH) specific surface area by 2 to pyrolysis is large particulate present invention CaO can be made.
Furthermore, since these substances are highly reactive and can be used in a method for absorbing or recovering toxic gases, they have many uses and have high industrial utility value.
Claims (3)
ＣａＯ＋Ｈ２Ｏ→Ｃａ（ＯＨ）2 （１）
で表される反応をさせるに際して、１気圧以上で６５０〜７００℃の水蒸気条件で反応（１）を進行させることにより、圧縮破壊強度が２５ｋｇ/cm 2 以上で粒子状を保持したままのCa(OH)2を生成させ、次いで、８５０℃〜９００℃で熱分解することを特徴とする比表面積が大きい粒子状CaOの製造方法。
Particulate calcium oxide (CaO) obtained by calcining limestone or calcium carbonate (CaCaO 3 ), wherein the particulate calcium oxide (CaO) has a particle diameter of 0.2 to 0.8 mm. Calcium oxide (CaO) reacts with water,
CaO + H 2 O → Ca (OH) 2 (1)
When the reaction represented by the formula (1) is performed, the reaction (1) is allowed to proceed under a water vapor condition of 650 to 700 ° C. at 1 atm or higher, so that the compressive fracture strength is 25 kg / cm 2 or more while maintaining the particulate form of Ca ( OH) 2 is produced, and then pyrolyzed at 850 ° C. to 900 ° C. A method for producing particulate CaO having a large specific surface area.
ＣａＯ＋Ｈ２Ｏ→Ｃａ（ＯＨ）2 （１）
で表される反応をさせるに際して、１気圧以上で６５０〜７００℃の条件で反応（１）を進行させることにより、圧縮破壊強度が２５ｋｇ/cm 2 以上で粒子状を保持したままのCa(OH)2を生成させ、次いで、それを８５０℃〜９００℃で熱分解して出来たCaOと、HCL,H2S,SO2,CO2,ハロゲンから選ばれる有害ガス(R)を、９００℃以下の温度で反応させ、Ca(R)を生成させるガス吸収方法。 Particulate calcium oxide (CaO) obtained by calcining limestone or calcium carbonate (CaCaO 3 ), wherein the particulate calcium oxide (CaO) has a particle diameter of 0.20 to 0.8 mm. Calcium oxide (CaO) reacts with water,
CaO + H 2 O → Ca (OH) 2 (1)
When the reaction represented by the formula (1) is carried out under the conditions of 650 to 700 ° C. at 1 atm or more, Ca (OH) with the compressive fracture strength of 25 kg / cm 2 or more and maintaining the particulate form is maintained. ) 2 and then pyrolyzing it at 850 ° C. to 900 ° C. and a harmful gas (R) selected from HCL, H 2 S, SO 2 , CO 2 and halogen at 900 ° C. A gas absorption method in which Ca (R) is produced by reacting at the following temperatures.
The Ca (R) produced by the gas absorption method according to claim 2 is treated with water vapor at a temperature of 100 ° C. to 800 ° C. and 1 atm to 100 atm, regenerated again into Ca (OH) 2 , and obtained Ca ( A gas recovery method that recovers high concentration of harmful gas (R) while reusing OH) 2 as a harmful gas absorbent.
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