JPH0521008B2 - - Google Patents
Info
- Publication number
- JPH0521008B2 JPH0521008B2 JP58223259A JP22325983A JPH0521008B2 JP H0521008 B2 JPH0521008 B2 JP H0521008B2 JP 58223259 A JP58223259 A JP 58223259A JP 22325983 A JP22325983 A JP 22325983A JP H0521008 B2 JPH0521008 B2 JP H0521008B2
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- gas
- water
- absorption tower
- halogen compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 150000002366 halogen compounds Chemical class 0.000 claims description 14
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 30
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011823 monolithic refractory Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Description
【発明の詳細な説明】
本発明は、石炭等の化石燃料の燃焼時に発生す
るSO2及びNOXを含有する排ガスをアンモニアの
存在下に炭素質材と接触させる脱硫脱硝プロセス
において、炭素質材の再生時に得られる高濃度
SO2含有ガス中に不純物として含まれるアンモニ
ア及びHClあるいはHF等のハロゲン化合物を除
去する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a desulfurization and denitrification process in which exhaust gas containing SO 2 and NO High concentration obtained during regeneration of
This invention relates to a method for removing ammonia and halogen compounds such as HCl or HF contained as impurities in SO 2 -containing gas.
この脱硫脱硝プロセスは、硫黄化合物等を吸着
して不活化した炭素質材の加熱再生時に得られる
脱離ガス中に高濃度で含まれるSO2を原料として
硫黄や硫酸等の副産物が回収できる点に特長があ
る。 This desulfurization and denitrification process uses SO 2 , which is highly concentrated in the desorbed gas obtained during heating and regeneration of carbonaceous materials that have been inactivated by adsorbing sulfur compounds, as a raw material, and can recover byproducts such as sulfur and sulfuric acid. It has its features.
本発明に基づく吸収装置の基本的機能は、特に
この脱離ガスを、最終的にクラウス装置で処理し
て硫黄として回収する方法に適用した場合に、非
常に明白である。 The basic function of the absorption device according to the invention is very clear, especially when applied to a process in which this desorbed gas is finally treated in a Claus device and recovered as sulfur.
現在、石炭専焼もしくは混焼ボイラの燃料炭に
は、発塵防止の為に海水が散布される場合が多
く、この為に、CI分やＦ分が燃料炭に付着して
いる。そして、この様な燃料炭を燃焼した排ガス
中には、SO2、NOXの他に、HCl、HF等のハロ
ゲン化合物が必然的に含まれている。 Currently, seawater is often sprayed onto the thermal coal in coal-fired or co-fired boilers to prevent dust generation, and as a result, CI and F components adhere to the thermal coal. The exhaust gas produced by burning such fuel coal inevitably contains halogen compounds such as HCl and HF in addition to SO 2 and NO X.
これらのハロゲン化合物は、SO2、NOXと共に
吸着剤である炭素質材に吸着されているので、そ
の脱離ガス中にも含まれている。それと同時に、
アンモニアを注入する脱硝法に於いて、炭素質吸
着剤には未反応のNH3が亜硫酸アンモニウム、
あるいは硫酸アンモニウム状にて吸着されている
ので、その脱離ガス中にはアンモニアが含まれて
いる。 These halogen compounds, along with SO 2 and NO At the same time,
In the denitrification method in which ammonia is injected, unreacted NH 3 is transferred to the carbonaceous adsorbent as ammonium sulfite.
Alternatively, since it is adsorbed in the form of ammonium sulfate, the desorbed gas contains ammonia.
これらのハロゲン化合物及びアンモニアは、装
置の腐食及び閉塞、及びクラウス装置内の触媒の
被毒等のトラブルの他に、クラウス触媒被毒に起
因するランニング・コストの上昇、及び単体硫黄
回収率の低下等のトラブルを引き起こす。 These halogen compounds and ammonia not only cause problems such as corrosion and blockage of the equipment and poisoning of the catalyst in the Claus apparatus, but also increase running costs due to Claus catalyst poisoning and decrease the recovery rate of elemental sulfur. causing other troubles.
本発明の目的は、上述の問題点に鑑み、上記の
トラブルをことごとく解決するようなSO2含有ガ
ス中のハロゲン及びアンモニアを除去する方法を
提供することにある。 In view of the above-mentioned problems, an object of the present invention is to provide a method for removing halogen and ammonia from SO 2 -containing gas, which solves all of the above-mentioned troubles.
すなわち、本発明の要旨とするところは、SO2
及びNOXを含有する排ガスをアンモニアの存在
下に炭素質材と接触させて脱硫脱硝を行い、硫黄
化合物等を吸着した炭素質材を再生する際に得ら
れるアンモニア、ハロゲン化合物及び水蒸気を含
むSO2含有ガスから、水を吸収剤として利用し、
アンモニア及びハロゲン化合物を除去する方法に
おいて、SO2含有ガスを、このSO2含有ガス中に
含まれる水蒸気を凝縮させた凝縮水が循環する吸
収塔に導き、凝縮水と接触させ、この凝縮水中に
アンモニア及びハロゲン化合物が選択的に吸収さ
れる温度まで温度調節することを特徴とするSO2
含有ガス中のアンモニア及びハロゲン化合物の除
去方法を提供することにある。 That is, the gist of the present invention is that SO 2
SO containing ammonia, halogen compounds, and water vapor obtained when exhaust gas containing NO 2 from the contained gas, using water as an absorbent,
In a method for removing ammonia and halogen compounds, SO 2 -containing gas is introduced into an absorption tower in which condensed water is circulated, in which water vapor contained in the SO 2 -containing gas is condensed, and brought into contact with the condensed water. SO 2 characterized by temperature adjustment to a temperature at which ammonia and halogen compounds are selectively absorbed.
An object of the present invention is to provide a method for removing ammonia and halogen compounds from contained gas.
以下に本発明の方法を詳細に説明する。 The method of the present invention will be explained in detail below.
第１図は本発明の方法における、ハロゲン及び
アンモニア吸収塔廻りのフローを示す。第１図に
おいて、１はハロゲン及びアンモニア吸収塔、２
は充填層、３はスプレー、４は循環水用ポンプ、
５は循環水冷却用熱交換器、６はブロー水用流量
調節弁、７は保有液レベル調節計である。 FIG. 1 shows the flow around the halogen and ammonia absorption tower in the method of the present invention. In Figure 1, 1 is a halogen and ammonia absorption tower, 2
is a packed bed, 3 is a spray, 4 is a circulating water pump,
5 is a heat exchanger for cooling circulating water, 6 is a blow water flow control valve, and 7 is a retained liquid level controller.
本発明に基づくハロゲン及びアンモニア吸収塔
（以下吸収塔という）１は、内部に、処理ガス中
に吸収剤である水を噴霧するスプレー３、及び気
液接触を促進する為の合成樹脂製の充填物２を備
えており、かつ内部の塔壁には特に、耐ハロゲン
性の合成樹脂ライニング、望ましくはテフロン・
ライニングを施こし、さらに、高温の処理ガス入
口部分には耐熱・耐酸性の不定形耐火物を内張り
した構造になつている。 The halogen and ammonia absorption tower (hereinafter referred to as absorption tower) 1 according to the present invention includes a spray 3 for spraying water as an absorbent into the treated gas, and a synthetic resin filling for promoting gas-liquid contact. In particular, the internal tower wall is lined with a halogen-resistant synthetic resin, preferably Teflon.
The structure is lined with a heat-resistant and acid-resistant monolithic refractory at the inlet of the high-temperature processing gas.
上記の如き吸収塔１に於いて、吸収塔下部より
吹き込まれた処理ガスは充填層２内を流下してき
た液滴と接触し、次いで吸収液が流下している充
填層２内を上昇していく間に、冷却され、処理ガ
ス中のハロゲン化合物及びアンモニアは、イオウ
化合物−ハロゲン化合物−アンモニア水蒸気系の
気液平衡関係に従つて、各々吸収液に吸収されて
いき、かつ処理ガス中の水蒸気が部分的に凝縮し
た後、吸収塔上部のガス出口より出て、後段の装
置に導入される。それと同時に吸収剤である水
は、吸収塔下部より抜き出され吸収塔内で凝縮し
た処理ガス中の水蒸気と同一量の循環水をブロー
水として抜き出した後、別途装置した冷却水を利
用した熱交換器５により冷却された後、吸収塔上
部のスプレー３により処理ガス中に噴霧される。 In the absorption tower 1 as described above, the processing gas blown from the lower part of the absorption tower comes into contact with droplets flowing down inside the packed bed 2, and then rises inside the packed bed 2 through which the absorption liquid is flowing down. Over time, the halogen compound and ammonia in the processing gas are cooled and absorbed into the absorption liquid according to the vapor-liquid equilibrium relationship of sulfur compound-halogen compound-ammonia water vapor system, and the water vapor in the processing gas After being partially condensed, it exits from the gas outlet at the top of the absorption tower and is introduced into the subsequent equipment. At the same time, the absorbent water is extracted from the lower part of the absorption tower, and the same amount of circulating water as the water vapor in the treated gas condensed in the absorption tower is extracted as blow water, and then heated using cooling water installed separately. After being cooled by the exchanger 5, it is atomized into the process gas by the spray 3 at the top of the absorption tower.
上記の如き吸収操作の場合、本発明に基づく吸
収塔では、イオウ化合物−ハロゲン化合物−アン
モニア−水蒸気系の気液平衡関係に従つて、吸収
剤である水の循環量及び温度を調節する事によ
り、ハロゲン及びアンモニアの大部分を吸収し、
かつ水蒸気を凝縮させ、かつSO2の吸収がほとん
ど起こらない様な操作条件を容易に実現する事が
出来る。 In the case of the above-mentioned absorption operation, in the absorption tower based on the present invention, the circulating amount and temperature of the absorbent water are adjusted according to the vapor-liquid equilibrium relationship of the sulfur compound-halogen compound-ammonia-steam system. , absorbs most of the halogens and ammonia,
Moreover, it is possible to easily realize operating conditions in which water vapor is condensed and SO 2 absorption hardly occurs.
すなわち、排ガス中の水蒸気を凝縮させ、外部
からの吸収剤としての水の添加を不要とすると共
に、上記排ガスからの凝縮水中にアンモニア及び
ハロゲン化合物を選択的に吸収させる温度まで温
度調節するのである。なお、運転初期等において
凝縮水が不足する場合には適宜外部より吸収水を
補給すればよい。 That is, the water vapor in the exhaust gas is condensed, making it unnecessary to add water as an absorbent from the outside, and the temperature is adjusted to a temperature that allows ammonia and halogen compounds to be selectively absorbed into the water condensed from the exhaust gas. . Note that if there is a shortage of condensed water at the beginning of operation, etc., absorbed water may be replenished from the outside as appropriate.
さらに、上記の如き吸収塔に於いて、処理ガス
の温度が200〜400℃であり、かつHCl濃度5000〜
8000ppm、HF濃度500〜2000ppm、NH3濃度
2000〜4000ppmであり、かつ水蒸気濃度20〜40％
である場合の望ましい実施例では、入口温度30〜
40℃、望ましくは31〜33℃に温度調節した吸収剤
である水を、液・ガス比3.5〜4.5／m3（Act）
望ましくは4.0〜4.2／m3（Act）なる量に流量
調節して、吸収塔上部のスプレーより処理ガス中
に噴霧する事により、処理ガス出口温度を40〜60
℃、望ましくは45〜55℃にまで冷却している。こ
の場合、HCl及びHFの除去率は90％以上であり、
かつNH3の除去率は85％以上であり、かつ処理
ガス中の水蒸気の80〜90％を凝縮させる事を達成
している。又、吸収処理後のブロー水は、公知の
アルカリ処理技術を利用して容易に処理してい
る。 Furthermore, in the absorption tower as described above, the temperature of the treated gas is 200 to 400°C, and the HCl concentration is 5000 to 400°C.
8000ppm, HF concentration 500-2000ppm, NH3 concentration
2000~4000ppm and water vapor concentration 20~40%
In a preferred embodiment, when the inlet temperature is 30~
Water, which is an absorbent, is temperature-controlled to 40℃, preferably 31 to 33℃, and the liquid/gas ratio is 3.5 to 4.5/m 3 (Act).
Preferably, the flow rate is adjusted to 4.0 to 4.2/m 3 (Act), and the treated gas is sprayed from the spray at the top of the absorption tower to a temperature of 40 to 60% at the treated gas outlet.
℃, preferably 45-55℃. In this case, the removal rate of HCl and HF is more than 90%,
Moreover, the removal rate of NH 3 is 85% or more, and it has been achieved that 80 to 90% of the water vapor in the treated gas is condensed. Further, the blow water after absorption treatment is easily treated using a known alkali treatment technique.
実施例
処理ガス組成H2O25〜30％、SO213〜15％、
N245〜50％、CO23〜５％、HCl5000〜6000ppm、
HF800〜1000ppm、NH32000〜3000ppmで、か
つ温度330〜350℃のガスを、内径200mmφ、全高
2000mmで、内部にスプレーと充填層を備えた吸収
塔に於いて、Ｌ／Ｇ＝4.0〜4.2／m3（Act）に
て運転したところ、出口に於いてガス温度50〜60
℃、HCl100ppm以下、HF60ppm以下、
NH310ppm以下であつた。Example Processing gas composition H 2 O 25-30%, SO 2 13-15%,
N 2 45-50%, CO 2 3-5%, HCl 5000-6000ppm,
Gases with HF800~1000ppm, NH 3 2000~3000ppm, and temperature 330~350℃, inner diameter 200mmφ, total height
When operating an absorption tower with a length of 2000 mm and a spray and a packed bed inside at L/G = 4.0 to 4.2/m 3 (Act), the gas temperature at the outlet was 50 to 60.
℃, HCl 100ppm or less, HF 60ppm or less,
NH 3 was less than 10 ppm.
第１図は、本発明の方法にもとづくアンモニア
及びハロゲン吸収塔廻りのフローを示す。
FIG. 1 shows the flow around the ammonia and halogen absorption tower based on the method of the present invention.
Claims (1)
の存在下に炭素質材と接触させて脱硫脱硝を行
い、硫黄化合物等を吸着した炭素質材を再生する
際に得られるアンモニア、ハロゲン化合物及び水
蒸気を含むSO2含有ガスから、水を吸収剤として
利用し、アンモニア及びハロゲン化合物を除去す
る方法において、SO2含有ガスを、このSO2含有
ガス中に含まれる水蒸気を凝縮させた凝縮水が循
環する吸収塔に導き、凝縮水と接触させ、この凝
縮水中にアンモニア及びハロゲン化合物が選択的
に吸収される温度まで温度調節することを特徴と
するSO2含有ガス中のアンモニア及びハロゲン化
合物の除去方法。1 Ammonia, halogen compounds, and water vapor obtained when exhaust gas containing SO 2 and NO In this method, water is used as an absorbent to remove ammonia and halogen compounds from an SO 2 -containing gas, in which condensed water, which is the condensation of water vapor contained in the SO 2 -containing gas, is circulated. A method for removing ammonia and halogen compounds from SO 2 -containing gas, which comprises introducing the gas into an absorption tower, bringing it into contact with condensed water, and adjusting the temperature to a temperature at which ammonia and halogen compounds are selectively absorbed into the condensed water. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58223259A JPS60118223A (en) | 1983-11-29 | 1983-11-29 | Removal of halogen and ammonia in sulfur compound- containing gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58223259A JPS60118223A (en) | 1983-11-29 | 1983-11-29 | Removal of halogen and ammonia in sulfur compound- containing gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60118223A JPS60118223A (en) | 1985-06-25 |
| JPH0521008B2 true JPH0521008B2 (en) | 1993-03-23 |
Family
ID=16795295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58223259A Granted JPS60118223A (en) | 1983-11-29 | 1983-11-29 | Removal of halogen and ammonia in sulfur compound- containing gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60118223A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10513466B2 (en) | 2017-01-16 | 2019-12-24 | Nuorganics LLC | System and method for recovering nitrogenous compounds from a gas stream |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2912145B2 (en) * | 1993-11-16 | 1999-06-28 | 住友重機械工業株式会社 | Purification method of sulfur oxide containing gas |
| JP2009082893A (en) * | 2007-10-03 | 2009-04-23 | Kanken Techno Co Ltd | Exhaust gas treating apparatus |
| EP2327467B1 (en) | 2008-02-22 | 2015-06-17 | Mitsubishi Heavy Industries, Ltd. | Apparatus for recovering co2 and method of recovering co2 |
| US10239016B2 (en) | 2016-12-07 | 2019-03-26 | Nuorganics LLC | Systems and methods for nitrogen recovery from a gas stream |
| CN109266402A (en) * | 2018-10-23 | 2019-01-25 | 唐钢美锦（唐山）煤化工有限公司 | A kind of do not stop production reduces the device and method of desulfurization pressure tower |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5261366A (en) * | 1976-11-02 | 1977-05-20 | Loewe Anstalt | Method of garbage treatment and apparatus thereof |
| JPS57196709A (en) * | 1981-05-27 | 1982-12-02 | Mitsubishi Heavy Ind Ltd | Removing method for halogen containing substance from desorbed gas used in dry desulfurization method |
-
1983
- 1983-11-29 JP JP58223259A patent/JPS60118223A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5261366A (en) * | 1976-11-02 | 1977-05-20 | Loewe Anstalt | Method of garbage treatment and apparatus thereof |
| JPS57196709A (en) * | 1981-05-27 | 1982-12-02 | Mitsubishi Heavy Ind Ltd | Removing method for halogen containing substance from desorbed gas used in dry desulfurization method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10513466B2 (en) | 2017-01-16 | 2019-12-24 | Nuorganics LLC | System and method for recovering nitrogenous compounds from a gas stream |
| US10934223B2 (en) | 2017-01-16 | 2021-03-02 | Nuorganics LLC | System and method for recovering nitrogenous compounds from a gas stream |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60118223A (en) | 1985-06-25 |
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