JPH03221592A - Operation of sulfuric acid facility - Google Patents
Operation of sulfuric acid facilityInfo
- Publication number
- JPH03221592A JPH03221592A JP2017612A JP1761290A JPH03221592A JP H03221592 A JPH03221592 A JP H03221592A JP 2017612 A JP2017612 A JP 2017612A JP 1761290 A JP1761290 A JP 1761290A JP H03221592 A JPH03221592 A JP H03221592A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- sulfuric acid
- ammonia
- phosphoric acid
- acidic
- 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.)
- Pending
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000002378 acidificating effect Effects 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 10
- 230000023556 desulfurization Effects 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 239000000571 coke Substances 0.000 claims abstract description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 8
- 239000003595 mist Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 abstract description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 4
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 4
- 239000007921 spray Substances 0.000 abstract description 3
- 239000004254 Ammonium phosphate Substances 0.000 abstract 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 abstract 1
- 235000019289 ammonium phosphates Nutrition 0.000 abstract 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Landscapes
- Industrial Gases (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はコークス炉ガスから硫酸を製造する方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing sulfuric acid from coke oven gas.
コークス炉ガスの脱硫で吸収除去されたＨ２Ｓの処理方
法は各種あるが、例えばモノエタノールアミンでＨｚ
Ｓを吸収するサルフィバン脱硫、炭酸ソーダで吸収する
バキュームカーボネート脱硫等の場合には吸収したＨ２
Ｓを酸性ガスとして追出し、これを燃焼して硫酸を製造
している。ところでこの酸性ガス中にはＨ，Ｓ、ＨｃＮ
、Ｃｏ２のほかＮＨ，も含まれている。燃焼によってＮ
Ｈ３から酸性並硫安を生威し、これが次工程で軟鉄製で
あるボイラーチューブの腐食、ボイラーチューブの閉塞
によるガス吸引の不態等を惹き起こす。この解決策とし
て従来はボイラー出口温度のアップ、ボイラーチューブ
材質の変更（例えばＳＵＳの使用）などがとられていた
。There are various methods for treating H2S absorbed and removed by desulfurization of coke oven gas, but for example, monoethanolamine is used to treat H2S.
In the case of Sulfiban desulfurization that absorbs S, vacuum carbonate desulfurization that absorbs with soda carbonate, etc., the absorbed H2
Sulfur is expelled as an acidic gas, which is then burned to produce sulfuric acid. By the way, this acidic gas contains H, S, and HcN.
, Co2 as well as NH. N by combustion
Acidic ammonium sulfate is generated from H3, which causes corrosion of the boiler tube made of soft iron in the next process, and gas suction failure due to blockage of the boiler tube. Conventional solutions to this problem include increasing the boiler outlet temperature and changing the material of the boiler tube (for example, using SUS).
〔発明が解決しようとする課題］
ボイラー出口温度を上昇させてもボイラーチューブの腐
食はやはり起こるため基本的な解決策ではない。一方、
ボイラーチューブの材質の変更はボイラーが高価になっ
てしまう。[Problems to be Solved by the Invention] Even if the boiler outlet temperature is increased, corrosion of the boiler tube still occurs, so this is not a fundamental solution. on the other hand,
Changing the material of the boiler tube makes the boiler more expensive.
本発明は、上記課題を解決するべくなされたものであり
、酸性ガスを燃焼する前に硫酸又はリン酸に吸収させて
、予め除去することによって目的を達成しうるものであ
る。The present invention has been made to solve the above problem, and can achieve the object by absorbing acid gas into sulfuric acid or phosphoric acid and removing it before burning the acid gas.
すなわち、本発明は、コークス炉ガスの脱硫によって生
成した硫化水素を含む酸性ガスを燃焼して硫酸を製造す
る方法において、酸性ガスを燃焼する前に該ガス中に含
まれているアンモニアを硫酸又はリン酸に吸収させて除
去することを特徴とする硫酸の製造方法に関するもので
ある。That is, the present invention provides a method for producing sulfuric acid by burning an acidic gas containing hydrogen sulfide produced by desulfurization of coke oven gas, and before burning the acidic gas, converts ammonia contained in the gas into sulfuric acid or The present invention relates to a method for producing sulfuric acid, which is characterized in that sulfuric acid is removed by absorption with phosphoric acid.
コークス炉ガスの脱硫方法は問うところではなく、Ｈ２
Ｓをガスとして分離するいかなる方式であってもよい。There is no question about the method of desulfurization of coke oven gas, but H2
Any method that separates S as a gas may be used.
酸性ガス中のアンモニアを硫酸又はリン酸で除去する手
段は、例えば充填塔、段塔、スプレー塔、スクラバー、
ぬれ壁塔のガス吸収塔を利用して行なえばよい。これら
のなかでスプレー塔が圧損がない点で特に好ましい。硫
酸及びリン酸の濃度は１〜２０％程度、好ましくは５〜
１５％程度が適当である。吸収率が不充分な場合には複
数のガス吸収塔を直列にして用いることにより吸収率を
高めることができ、また、複数組を並列にして用いるこ
とにより連続操業を確保することができる。アンモニア
を除去した後は必要によりミストセパレータ等で硫酸又
はリン酸のミストを除去し燃焼炉に入れて燃焼すればよ
い。一方、アンモニアを吸収した液からは硫安又はリン
安を回収することができる。Means for removing ammonia in acidic gas with sulfuric acid or phosphoric acid include, for example, packed towers, plate towers, spray towers, scrubbers,
This can be done by using a gas absorption tower that is a wet wall tower. Among these, spray towers are particularly preferred since there is no pressure drop. The concentration of sulfuric acid and phosphoric acid is about 1 to 20%, preferably 5 to 20%.
Approximately 15% is appropriate. If the absorption rate is insufficient, the absorption rate can be increased by using a plurality of gas absorption towers in series, and continuous operation can be ensured by using multiple sets in parallel. After removing ammonia, if necessary, the mist of sulfuric acid or phosphoric acid may be removed using a mist separator or the like, and the mixture may be placed in a combustion furnace and burned. On the other hand, ammonium sulfate or ammonium phosphorus can be recovered from the liquid that has absorbed ammonia.
［作用］
脱硫設備の蒸留塔から追い出される酸性ガス中には、Ｈ
，Ｓ、Ｃｏ、、ＨｃＮ、ＮＨ３等が含まれる。[Operation] There is H in the acid gas expelled from the distillation column of the desulfurization equipment.
, S, Co, , HcN, NH3, etc.
このガスを燃焼すると下記の反応により、Ｈ，Ｓ＋０２
→ Ｓ Ｏ２＋ Ｓ ＣｈＳＯ３＋ＨｚＯ＋ＮＨｘ
→ ＮＨ，Ｈ３Ｏ。When this gas is burned, H, S+02
→ S O2+ S ChSO3+HzO+NHx
→ NH, H3O.
酸性亜硫安（ＮＨ，Ｈ３Ｏ４）が生成する。この酸性亜
硫安は腐食性が大きい。そこで、燃焼炉に入れる前にＨ
２ＳＯ４又はＨ，ＰＯ，溶液により吸収させる。Acidic ammonium sulfite (NH, H3O4) is produced. This acidic ammonium sulfite is highly corrosive. Therefore, before putting it into the combustion furnace,
Absorb with 2SO4 or H, PO, solution.
２ Ｎ Ｈ３＋ Ｈｚ Ｓ Ｏａ → （ＮＨ，）Ｚ
ＳＯ。2 N H3+ Hz S Oa → (NH,)Z
S.O.
ＮＨｉ＋ＨｉＰＯ４→ ＮＨ，Ｈ２ＰＯ４〔実施例〕
第１図に示す設備を用いた。この設備は酸性ガス吸収塔
１及び蒸留塔２よりなる脱硫設備、アンモニア除去塔３
よりなるアンモニア除去設備並びに燃焼炉４、ボイラー
５及び冷却塔６よりなる硫酸設備からなっている。NHi+HiPO4→NH,H2PO4 [Example] The equipment shown in FIG. 1 was used. This equipment consists of a desulfurization equipment consisting of an acid gas absorption tower 1 and a distillation tower 2, and an ammonia removal tower 3.
The system consists of an ammonia removal facility consisting of a combustion furnace 4, a boiler 5, and a cooling tower 6.
脱硫設備はサルフィバンプロセスによるものであり、コ
ークス炉ガス７は酸性ガス吸収塔１の下部から送入され
、酸性ガスが吸収除去されて上部から出される。酸性ガ
ス吸収剤であるモノエタノールアミンは熱交換器８で熱
交換された後、酸性ガス吸収塔１へ送入され、酸性ガス
を吸収し塔１の下部から抜き出される。この酸性ガスを
吸収したモノエタノールアミンは熱交換器８で熱交換し
て加熱され蒸留塔２に上部から入る。蒸留塔２の下部か
らは水蒸気９を吹込んでモノエタノールアミンから酸性
ガスを蒸発させる。この酸性ガスを熱交換器１０で熱交
換して冷却し、アンモニア除去塔３に送入する。そこで
１０％硫酸水溶液１１のシャワーで洗浄されてアンモニ
アを吸収除去され、ミストセパレータ１２に送られる。The desulfurization equipment is based on the sulfiban process, and the coke oven gas 7 is fed from the lower part of the acid gas absorption tower 1, the acid gas is absorbed and removed, and the coke oven gas 7 is discharged from the upper part. Monoethanolamine, which is an acidic gas absorbent, undergoes heat exchange in a heat exchanger 8, and then is sent to an acidic gas absorption tower 1, absorbs acidic gas, and is extracted from the bottom of the tower 1. The monoethanolamine that has absorbed this acidic gas is heated by heat exchange in a heat exchanger 8, and then enters the distillation column 2 from above. Steam 9 is blown into the bottom of the distillation column 2 to evaporate acidic gas from monoethanolamine. This acidic gas is cooled by exchanging heat with a heat exchanger 10, and then sent to the ammonia removal tower 3. There, it is washed with a shower of 10% sulfuric acid aqueous solution 11 to absorb and remove ammonia, and is sent to the mist separator 12.
一方、アンモニアを吸収した硫酸水溶液は硫酸水溶液槽
１３に戻り、熱交換器１４を経てアンモニア除去塔３へ
循環される。アンモニアの濃度が高くなってきたら一部
あるいは全部を抜き出して硫安製造工程等へ送り、不足
分の硫酸水溶液を補充する。ミストセパレータ１２でミ
ストを分離された酸性ガスは燃焼炉４で燃焼されてＨ，
ＳがＳＯ３に変わり、燃焼により発生した熱はボイラー
５で熱交換され、冷却塔６で冷却されて硫酸となる。On the other hand, the sulfuric acid aqueous solution that has absorbed ammonia returns to the sulfuric acid aqueous solution tank 13 and is circulated to the ammonia removal column 3 via the heat exchanger 14. When the concentration of ammonia becomes high, part or all of it is extracted and sent to an ammonium sulfate manufacturing process, and the shortage is replenished with an aqueous sulfuric acid solution. The acidic gas from which the mist has been separated by the mist separator 12 is burned in the combustion furnace 4 to produce H,
S turns into SO3, and the heat generated by combustion is exchanged in the boiler 5 and cooled in the cooling tower 6 to become sulfuric acid.
上記装置において生成した酸性ガスは、Ｈ２Ｓ１９．０
％、Ｃｏｔ６０．２％、ＨＣＮ２．５％、ＮＨ３０，１
１％を含んでいた。このガスをアンモニア除去塔３で１
０％硫酸シャワーで洗浄したところ、この塔３の出口ガ
スの組成はＨ，Ｓ １９．０％、Ｃ０，６０，２％、Ｈ
ＣＮ２．５％、Ｎ Ｈ，０，００５％であった。このガ
スを通常の運転条件で操業して硫酸を製造したところ、
ボイラーチューブ等装置の材質が軟鉄であるにもかかわ
らず、３力月間の連続操業でチューブの腐食及び付着物
はほとんど生じなかった。The acidic gas generated in the above device is H2S19.0
%, Cot60.2%, HCN2.5%, NH30.1
It contained 1%. This gas is removed by ammonia removal tower 3.
When washed with a 0% sulfuric acid shower, the composition of the outlet gas from this column 3 was H, S 19.0%, C0, 60,2%, H
CN was 2.5% and NH was 0,005%. When this gas was operated under normal operating conditions to produce sulfuric acid,
Despite the boiler tubes and other equipment being made of soft iron, there was almost no corrosion or deposits on the tubes during three months of continuous operation.
〔発明の効果］
本発明の方法により、ボイラーチューブの腐食速度を大
巾に減少させることができた。また、ボイラーチューブ
への酸性亜硫安の付着も減少させることができ、それに
よってチューブの閉塞問題を解消することができた。さ
らに、伝熱効率も向上させることができた。[Effects of the Invention] By the method of the present invention, the corrosion rate of boiler tubes could be significantly reduced. It was also possible to reduce the adhesion of acidic ammonium sulfite to the boiler tubes, thereby solving the tube clogging problem. Furthermore, heat transfer efficiency was also improved.
第１図は本発明の方法に使用される装置の一例の概略を
示す図である。FIG. 1 is a diagram schematically showing an example of an apparatus used in the method of the present invention.
Claims (1)
酸性ガスを燃焼して硫酸を製造する方法において、酸性
ガスを燃焼する前に該ガス中に含まれているアンモニア
を硫酸又はリン酸に吸収させて除去することを特徴とす
る硫酸の製造方法In a method for producing sulfuric acid by burning acidic gas containing hydrogen sulfide produced by desulfurization of coke oven gas, ammonia contained in the gas is absorbed into sulfuric acid or phosphoric acid before burning the acidic gas. A method for producing sulfuric acid characterized by removing
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017612A JPH03221592A (en) | 1990-01-26 | 1990-01-26 | Operation of sulfuric acid facility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017612A JPH03221592A (en) | 1990-01-26 | 1990-01-26 | Operation of sulfuric acid facility |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03221592A true JPH03221592A (en) | 1991-09-30 |
Family
ID=11948709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017612A Pending JPH03221592A (en) | 1990-01-26 | 1990-01-26 | Operation of sulfuric acid facility |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03221592A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111078C (en) * | 1999-12-30 | 2003-06-11 | 赵善茂 | Complex utilization method for boiler fume |
| JP2012523309A (en) * | 2009-04-08 | 2012-10-04 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Method and apparatus for treating an acid gas stream |
| CN108786405A (en) * | 2018-07-03 | 2018-11-13 | 朱国琴 | A kind of flue gas desulfurization device in thermal power plant |
-
1990
- 1990-01-26 JP JP2017612A patent/JPH03221592A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111078C (en) * | 1999-12-30 | 2003-06-11 | 赵善茂 | Complex utilization method for boiler fume |
| JP2012523309A (en) * | 2009-04-08 | 2012-10-04 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Method and apparatus for treating an acid gas stream |
| CN108786405A (en) * | 2018-07-03 | 2018-11-13 | 朱国琴 | A kind of flue gas desulfurization device in thermal power plant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5318758A (en) | Apparatus and process for removing carbon dioxide from combustion exhaust gas | |
| US5480619A (en) | Regenerative scrubber application with condensing heat exchanger | |
| SU1537125A3 (en) | Method of purifying gas from hydrogen sulfide and carbon dioxide | |
| CN103936036B (en) | Integrated carbon dioxide removes and ammonia-soda process | |
| JP2023508656A (en) | Control of aerosol formation during absorption in ammonia-based desulfurization | |
| KR101839225B1 (en) | Method for purification of coke oven gas and device for purification of coke oven gas | |
| CA2840755C (en) | Chilled ammonia based co2 capture system with ammonia recovery and processes of use | |
| EP3042712B1 (en) | Recovery unit for recovering co2 and/or h2s | |
| WO2013039041A1 (en) | Co2 recovery device and co2 recovery method | |
| EP2405989A1 (en) | Method and plant for amine emission control | |
| KR101937801B1 (en) | Method and apparatus for removing carbon dioxide and SOx from flue gas | |
| JP6021932B2 (en) | CO2 recovery apparatus and CO2 recovery method | |
| US10953361B2 (en) | CO2 recovery device and recovery method | |
| CN203033778U (en) | Device for producing ammonium sulfate by using sulfate pulp and ammonia water as raw materials | |
| JPH03221592A (en) | Operation of sulfuric acid facility | |
| US8986640B1 (en) | System and method for recovering ammonia from a chilled ammonia process | |
| CN202808740U (en) | Efficient CO2 collecting device based on IGCC (integrated gasification combined cycle) before combustion | |
| CN112675669A (en) | Device and method for removing sulfur oxides in high-humidity flue gas | |
| JPS60118223A (en) | Removal of halogen and ammonia in sulfur compound- containing gas | |
| CN212327909U (en) | High-temperature flue gas desulfurization and denitrification dust removal system | |
| JPS6287227A (en) | Dry stack gas desulfurization method | |
| IT202000020473A1 (en) | SYSTEM AND METHOD OF ABATEMENT OF CARBON DIOXIDE BASED ON AMMONIA, AND DIRECT CONTACT COOLER FOR THEM | |
| JPH03161023A (en) | Treatment of hydrogen sulfide-containing non-condensed gas | |
| JP2001046834A (en) | Limestone/gypsum desulfurizing apparatus | |
| JPH0249124B2 (en) |