JP6715030B2 - 排ガスから二酸化炭素および二酸化硫黄を触媒除去する方法 - Google Patents
排ガスから二酸化炭素および二酸化硫黄を触媒除去する方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 48
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 10
- 239000001569 carbon dioxide Substances 0.000 title description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 239000003054 catalyst Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000011049 filling Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
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- 238000005406 washing Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 50
- 238000012360 testing method Methods 0.000 description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 31
- 238000000926 separation method Methods 0.000 description 12
- UPWPBIUUSLIWAI-UHFFFAOYSA-N [4-(4-aminophenyl)sulfonylphenyl]urea Chemical compound C1=CC(NC(=O)N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 UPWPBIUUSLIWAI-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000003464 sulfur compounds Chemical class 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical class [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 5
- 150000001722 carbon compounds Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 2
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/818—Employing electrical discharges or the generation of a plasma
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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
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Description
・SO2で活性炭を充填させる工程、
・水で排ガスを充填または部分的に充填させる工程、
・排ガスを反応器に導入する工程、
・同じ触媒上で、SO2をH2SO4へと接触転化させ、そしてそれと並行して、CO2をCおよびO2へと接触転化させる工程、および/またはCを硫黄化合物に加える工程、
・その触媒を洗い落とし、そして液体としてH2SO4を排出し、また、固体として炭素を、または/かつ硫黄化合物に結合された炭素を排出する工程
によって特徴付けられる、活性炭触媒で充填されている反応器において排ガスから二酸化炭素および二酸化硫黄を触媒除去する方法により、本発明にしたがって達成される。
・クエンチングによる反応器へ入る前の排ガスの水充填
・煙道ガスのSO2含量300ppm〜6000ppm
この場合、理想状態では、そして連続運転によって、このSO2の174〜3480ppmのみが、CO2転化中に転化され得る、ことに留意すべきである。この場合、過剰のSO2は、H2SO4酸形成のために使用されるか、またはSO2/SO3の形態で大気中に排出される。
・0.1体積%(1000ppm)〜15体積%(150000ppm)の煙道ガスのCO2含量
・10〜80℃のガス温度
・O2含量約20体積%
・クエンチングによる排ガスの水充填と冷却
・試験した触媒は、Norit_PK1−3、Norit_PK_2−4、およびNorit_PK_3−5の名称で、Postbus 105 NL−3800 AC AmersfootにあるNORIT Nederland B.V.によって提供された。
SO2+1/2O2+nH2O(触媒的に)→H2SO4+(n−1)H2O
・O2およびSO2は、SO3へと改質される触媒の活性中心の方へと移動する。
・SO3は、触媒の活性中心から外に移動し、触媒コア周囲の水性被覆とH2SO4を形成する。
・SO2は、酸素および水と反応して、上記の反応方程式にしたがって、硫酸を形成する。
・SO2分子とおおよそ同一サイズであるCO2分子も、触媒コアの細孔中に輸送され、そしてそこで、生成エネルギーが加えられることによって分離し、そして硫黄化合物上に吸着される。
コア周囲の水性被覆において生じる濃硫酸は、高い液面張力(比表面積)によって、CO2のC部分およびO2を吸着する。而して、「炭素−硫黄化合物」は、このようにして生成される。とりわけ、以下の反応が起こる:
CO2 + SO2 + H2O → C + H2SO4 + 1/2O2
H2SO4 + CO2 → SCO3 + H2O + O2
・硫黄化合物上にあるC部分は、懸濁液として硫酸中に提供される。
・形成された炭素化合物は、水で洗浄し、而して硫酸を希釈することによって、触媒からの硫酸を有する懸濁液中に、排出する。形成された炭素化合物は、短時間の後に、沈殿を形成した。
試験1:
試験2
10 試験反応器
12 下部
14 上部
16 加熱装置
18、20 加圧シリンダー
22、24 弁
26 第一測定器
28 冷却器
30 排ガス送風機
32 活性炭触媒
34 第二測定器
36 貯蔵容器
38 計量装置
40 ポンプ
42 容器
44 測定器
46 ポンプ
48 測定器
Claims (8)
- 活性炭触媒によって充填された反応器中においてSO 2 およびCO 2 を含む排ガスからSO 2 およびCO 2 を触媒除去する方法であって、以下の工程:
・SO2で前記活性炭触媒を充填させる工程、
・水で前記排ガスを充填または部分的に充填させる工程、
・前記反応器中に前記排ガスを導入する工程、
・前記活性炭触媒上で、SO2をH2SO4へと接触転化させる工程、
・SO2のH2SO4への接触転化中に生成される発熱エネルギーによってCO2を前記排ガスから除去する工程、
・前記活性炭触媒を洗い落とし、そして液体としてH2SO4を排出する工程、
を順に行うことを特徴とする、方法。 - 前記排ガス中のSO2およびCO2の割合が、0.25〜0.58モル/モルであることを特徴とする、請求項1に記載の方法。
- 前記排ガスの入口温度が、周囲温度から150℃までであることを特徴とする、請求項1または請求項2に記載の方法。
- 前記排ガスのO2含量が、前記排ガスのSO2含量に比べて8倍を超えることを特徴とする、請求項1〜3のいずれか一項に記載の方法。
- 前記排ガスが、クエンチングによって水で充填されることを特徴とする、請求項1〜4のいずれか一項に記載の方法。
- 軟化水または脱塩水を使用して前記活性炭触媒を洗い流すことを特徴とする、請求項1〜5のいずれか一項に記載の方法。
- 前記活性炭触媒が、前記排ガスに対して向流または並流で洗い流されることを特徴とする、請求項1〜6のいずれかに一項に記載の方法。
- 前記活性炭触媒のSO2除去率が、0.4〜0.6であることを特徴とする、請求項1〜7のいずれか一項に記載の方法。
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LU91685A LU91685B1 (de) | 2010-05-07 | 2010-05-07 | Verfahren zur katalytischen Entfernung von Kohlendioxyd und Schwefeldioxid aus Abgasen |
LU91685 | 2010-05-07 |
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JP2016034166A Active JP6715030B2 (ja) | 2010-05-07 | 2016-02-25 | 排ガスから二酸化炭素および二酸化硫黄を触媒除去する方法 |
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LU91900B1 (de) | 2011-11-14 | 2013-05-15 | Carbon Process & Plant Engineering S A | Verfahren zur katalytischen Entfernung von Kohlendioxyd NOx aus Abgasen |
US8877152B2 (en) * | 2013-02-27 | 2014-11-04 | Alstom Technology Ltd | Oxidation system and method for cleaning waste combustion flue gas |
LU92547B1 (de) | 2014-09-17 | 2016-03-18 | Cppe Carbon Process & Plant Engineering S A | Verfahren zur katalytischen entfernung von schwefeldioxid aus abgasen |
TWI569866B (zh) * | 2015-04-07 | 2017-02-11 | 中國鋼鐵股份有限公司 | 自動化二氧化碳吸收裝置及其方法 |
LU93012B1 (en) | 2016-04-04 | 2017-11-08 | Cppe Carbon Process & Plant Eng S A En Abrege Cppe S A | Sulfur dioxide removal from waste gas |
LU93014B1 (en) | 2016-04-04 | 2017-10-05 | Ajo Ind S A R L | Catalyst mixture for the treatment of waste gas |
LU93013B1 (en) | 2016-04-04 | 2017-11-08 | Cppe Carbon Process & Plant Eng S A En Abrege Cppe S A | Process for the removal of heavy metals from fluids |
CN107326390B (zh) * | 2017-06-09 | 2019-03-26 | 中国矿业大学 | 一种阳极氧化强化二氧化碳还原的装置及其方法 |
LU100469B1 (en) | 2017-10-09 | 2019-04-09 | Cppe Carbon Process & Plant Eng S A | Elimination of SO2 and CO2 from a gas |
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LU91685B1 (de) | 2011-11-08 |
CA2797144A1 (en) | 2011-11-10 |
ZA201208968B (en) | 2013-08-28 |
EA021534B1 (ru) | 2015-07-30 |
TN2012000519A1 (en) | 2014-04-01 |
CN102892484B (zh) | 2014-12-10 |
CA2797144C (en) | 2017-08-08 |
BR112012028256A2 (pt) | 2017-03-14 |
SG185469A1 (en) | 2012-12-28 |
JP2016165714A (ja) | 2016-09-15 |
CN102892484A (zh) | 2013-01-23 |
AU2011249726A1 (en) | 2013-01-10 |
MX2012012878A (es) | 2013-04-03 |
US8535631B2 (en) | 2013-09-17 |
TW201204457A (en) | 2012-02-01 |
AU2011249726B2 (en) | 2014-09-18 |
MA34257B1 (fr) | 2013-05-02 |
KR20130084979A (ko) | 2013-07-26 |
EP2566603A1 (de) | 2013-03-13 |
JP2013525107A (ja) | 2013-06-20 |
CL2012003099A1 (es) | 2013-06-14 |
DK2566603T3 (da) | 2014-05-19 |
AR081013A1 (es) | 2012-05-30 |
EA201291164A1 (ru) | 2013-04-30 |
EP2566603B1 (de) | 2014-03-12 |
US20130108533A1 (en) | 2013-05-02 |
TWI510282B (zh) | 2015-12-01 |
ES2471882T3 (es) | 2014-06-27 |
WO2011138425A1 (de) | 2011-11-10 |
PL2566603T3 (pl) | 2014-07-31 |
JP2018027540A (ja) | 2018-02-22 |
UY33371A (es) | 2011-12-01 |
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