JPH08506993A - Method and apparatus for absorbing hydrogen sulfide - Google Patents
Method and apparatus for absorbing hydrogen sulfideInfo
- Publication number
- JPH08506993A JPH08506993A JP6518871A JP51887194A JPH08506993A JP H08506993 A JPH08506993 A JP H08506993A JP 6518871 A JP6518871 A JP 6518871A JP 51887194 A JP51887194 A JP 51887194A JP H08506993 A JPH08506993 A JP H08506993A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- gas
- hydrogen sulfide
- carbonate
- stage
- 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
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 87
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 119
- 239000007789 gas Substances 0.000 claims abstract description 88
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000010521 absorption reaction Methods 0.000 claims abstract description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 38
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 29
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012670 alkaline solution Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 14
- 230000036961 partial effect Effects 0.000 claims abstract description 5
- 239000000155 melt Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 abstract description 11
- 230000008020 evaporation Effects 0.000 abstract description 11
- 238000007599 discharging Methods 0.000 abstract description 4
- 238000012856 packing Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 6
- -1 Therefore Chemical compound 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 241000180579 Arca Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- B01D53/52—Hydrogen sulfide
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
- D21C11/08—Deodorisation ; Elimination of malodorous compounds, e.g. sulfur compounds such as hydrogen sulfide or mercaptans, from gas streams
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
(57)【要約】 黒液蒸発において発生した、硫化水素ならびに二酸化炭素を含むガス（３）から、液体吸収により、硫化水素を選択的に除去する方法および装置を開示する。本方法では、ガスが向流で、循環する炭酸塩含有アルカリ溶液、好ましくは炭酸ナトリウム溶液（２５）、と好ましくは３つの段階（６、７、８）からなる多段階で接触し、溶液のpHが、水酸化物、好ましくは水酸化ナトリウム溶液（２６、２７、２８）、を加えることにより吸収の際に約９〜１２に調節される。互いに接触する時、ガスは乱流で、液体は層流であるのが好ましい。装置は、ガスの入口（２）、ガスの出口（４）、および幾つかの連続する段階（６、７、８）に配置された充填物（９）を有する容器（１）を含む。本装置は、炭酸塩含有溶液を最後の段階に供給し、この段階を通して向流でガスに供給し、溶液をその段階に循環させる手段（２５）、溶液の部分流をある段階からその前の段階に供給するための、段階間に配置された導管（２９、３０）、これらの段階（６、７、８）の少なくとも一つで水酸化物を炭酸塩含有溶液に供給する手段（２６、２７、２８）、およびスルフィド含有液体を排出するための、ガスの供給方向で見て最初の段階からの出口導管（３１）を有する。 (57) [Summary] Disclosed is a method and apparatus for selectively removing hydrogen sulfide from a gas (3) containing hydrogen sulfide and carbon dioxide generated in black liquor evaporation by liquid absorption. In this method, the gas is contacted countercurrently with a circulating carbonate-containing alkaline solution, preferably sodium carbonate solution (25), in multiple stages, preferably consisting of three stages (6, 7, 8), The pH is adjusted to about 9-12 during absorption by adding a hydroxide, preferably sodium hydroxide solution (26, 27, 28). When in contact with each other, the gas is preferably turbulent and the liquid is laminar. The device comprises a container (1) with a gas inlet (2), a gas outlet (4) and a packing (9) arranged in several successive stages (6, 7, 8). The device comprises means for feeding a carbonate-containing solution to the last stage, countercurrently feeding the gas through this stage, and circulating the solution to that stage (25), a partial stream of solution from one stage to the previous. Conduits (29, 30) arranged between the stages for feeding the stages, means for feeding the hydroxide to the carbonate-containing solution (26, at least one of these stages (6, 7, 8)) 27, 28), and an outlet conduit (31) from the first stage in the gas feed direction for discharging the sulphide-containing liquid.
Description
【発明の詳細な説明】 硫化水素の吸収方法および装置 本発明は、硫化水素の吸収方法および装置、より詳しくは黒液蒸発において液体 吸収により、硫化水素ならびに二酸化炭素を含むガスから硫化水素を選択的に除 去する方法および装置に関する。 硫化水素は、主として硫化水素イオン（ＨＳ-）の形態で吸収されるが、スル フィドイオン（Ｓ2-）の形態でも吸収される。以下、これらのイオンの総含有量 を総括的に“総スルフィド含有量”またはより短く“スルフィド含有量”と呼ぶ 。 硫化水素は、水酸化ナトリウムの様なアルカリ水溶液に吸収させることにより 、あるいはエタノールアミン、例えばモノエタノールアミンおよびジエタノール アミン、を使用することにより、硫化水素含有ガスから除去できることが良く知 られている。この吸収方法は、例えば、純粋な形態の硫化水素の製造、および所 望によりさらにクラウス製法における硫黄の処理に使用することができる。ガス が硫化水素に加えて二酸化炭素を含む場合、その二酸化炭素もアルカリ溶液に吸 収される。二酸化炭素は水に対する溶解性が硫化水素とほぼ同じであり、したが って二酸化炭素は硫化水素と競合して溶液に吸収される。硫化水素および二酸化 炭素は、例えば水酸化ナトリウムのアルカリ水溶液に下記の式にしたがって吸収 される。 Ｈ2Ｓ＋ＯＨ- → ＨＳ-＋Ｈ2Ｏ （１） Ｈ2Ｓ＋２ＯＨ- → Ｓ2-＋２Ｈ2Ｏ （２） ＣＯ2＋ＯＨ- → ＨＣＯ3 - （３） ＣＯ2＋２ＯＨ- → ＣＯ3 2-＋Ｈ2Ｏ （４） 硫化水素に対する選択性、すなわち吸収される硫化水素のモル数と吸収される （硫化水素＋二酸化炭素）のモル数の比は、そのガスの硫化水素および二酸化炭 素含有量に正比例する。そのため、二酸化炭素に関する競合は、実際のほとんど の場合がそうである様に、ガスが硫化水素より多くの二酸化炭素を含む場合に特 に顕著である。ガスが例えば１体積％の硫化水素および１０体積％の二酸化炭素 を含み、硫化水素を水酸化ナトリウム溶液で吸収しようとする場合、硫化水素の 選択性は１０％に過ぎない、すなわち吸収されるガスの９０％は二酸化炭素であ る、つまり水酸化ナトリウムの９０％が二酸化炭素の吸収に費やされる。 硫化水素ならびに二酸化炭素を含むガスから硫化水素を吸収する際の上記の不 都合を改善するために、硫化水素を選択的に吸収する方法が開発されている。例 えば、過マンガン酸カリウム、重クロム酸ナトリウムまたは第二鉄塩の様な強酸 化剤の溶液に硫化水素を選択的に吸収させる努力がなされている。他の選択的方 法では、炭酸ナトリウムまたは炭酸カリウムの様なアルカリ溶液を使用し、吸収 における操作条件を注意深く調整している。この先行技術に関するより詳細な情 報は、C．Oloman、F.E．Murray およびJ.B．Riskによる“煙道ガスからの硫化水 素の選択的吸収”と題する記事、Pulp and Paper Magazine of Canada、１９６ ９年１２月５日、６９頁以降、ならびにE．Bendall、R.C．AikenおよびF．Manda s による“微小噴霧における吸収および反応による、大量のＣＯ2からのＨ2Ｓの 選択的吸収”と題する記事、AICHE Journal（Vol．29，No，1）、１９８３年１ 月、６６頁以降に記載されている。 先行技術の一例は、例えば黒液の燃焼で発生する炉ガスから硫黄を回収する方 法に関するＵＳ−３，５５４，８５９に記載されている。硫化水素および二酸化 炭素を含む燃焼ガスは、分子状酸素を含むガスと、および、例えば水酸化ナトリ ウムおよび炭酸ナトリウムまたは炭酸ナトリウムおよび炭酸水素ナトリウムの形 態のナトリウムイオンを含むアルカリ水溶液と接触する。こうして、硫化水素は ガスから吸収され、チオ硫酸塩に酸化される。この吸収は、酸化第二鉄の添加に よりさらに効果的になり、こうして溶液のスルフィド濃度は非常に低い水準に維 持される、すなわち溶液のスルフィド濃度は最小に抑えられる。 水酸化ナトリウム溶液の様な水酸化物溶液の代わりに、炭酸ナトリウム溶液の 様な炭酸塩溶液を使用することにより、硫化水素の吸収選択性は約３０〜５０％ 増大する。その様な吸収の際に起こる反応は一般的に次の様に表わされる。 吸収溶液が炭酸塩溶液である場合、硫化水素はほとんど瞬間的に吸収されるの に対し、二酸化炭素は炭酸塩イオンと極めてゆっくりと反応し、炭酸水素塩イオ ンを形成する。吸収媒体として炭酸塩溶液を使用する場合、高濃度の炭酸水素塩 が生じるので、上記の平衡式（６）から明らかな様に、二酸化炭素の吸収に対す る“反対圧”（平衡圧）の利点がさらに得られる。 吸収媒体として炭酸塩溶液を使用する場合に生じる問題は、炭酸水素塩イオン の形成により引き起こされる吸収容量の低下により、溶液中に比較的低いスルフ ィド含有量しか達成されない、ということである。そのため、約０．３０モル/l を超えるスルフィド含有量を得るのは極めて困難である。その結果、炭酸塩溶液 の形態の吸収媒体を使用して硫化水素を選択的に吸収する先行技術の方法は、硫 化水素含有および二酸化炭素含有ガスが発生する多くの分野でその様な方法に対 する大きな需要があるにもかかわらず、あまり成果を上げていない。その様な応 用分野の例は、石油精製、石炭ガス製造、および特に硫酸塩パルプ工業で行なわ れる黒液の燃焼である。 従来のトムリンソン法により硫酸塩工業で化学物質を回収する場合、黒液をソ ーダ回収装置で燃焼させ、蒸気を発生させ、主として炭酸ナトリウムおよび硫化 ナトリウムからなる溶融物を形成する。次いで溶融物を水に溶解させ、苛性化し 、 炭酸ナトリウムを水酸化ナトリウムに転化させ、白液をえるが、その白液は木の 消化に再使用することができる。ソーダ回収装置の管が破裂した時の爆発の危険 性を始めとする多くの理由から、近年、黒液を還元条件下で熱分解させ、溶融物 が形成されない、黒液燃焼のための新しい方法を開発する努力がなされている。 その様な方法は総括的に“黒液蒸発”と呼ばれるが、その一例はいわゆるSCA-Bi llerud法である（E．HorntvedtおよびJ．Gomy、Paper Trade Journal 158(1974) 16、３２〜３４頁）。この方法では、反応器中で黒液を、主として炭酸ナトリウ ムおよび炭素からなる粉塵および特に硫黄化合物を含む可燃性ガスが形成される 様な温度条件下で、熱分解させる。黒液蒸発の別の例は、化学量論的に必要な量 よりも少ない量で酸素を同時に供給し、１０バールを超える圧力で、溶融物が形 成されない様な温度で黒液を熱分解させる方法に関するＵＳ−４，８７２，９５ ０に開示されている。蒸発により、主として炭酸ナトリウムからなる固体相、お よび主として硫化水素、一酸化炭素、二酸化炭素、水素、水蒸気、およびメタン からなる気体相が形成される。 ＥＰ ４５９，９６２は、黒液蒸発における処理ガスの浄化に関する。この浄 化では、硫化水素イオンおよび水酸化物イオンを含むアルカリ溶液と接触させる ことにより、ガスから硫黄化合物およびナトリウム化合物が除去される。浄化に は少なくとも２つの工程が関与する。第一工程では、ガスはアルカリ溶液と共に ベンチュリノズルを通過し、ガス中の黒液の溶融したエーロゾル滴が溶液により 吸収される。次いで、ガスは、水酸化物イオンおよび硫化水素イオンを４：１を 超えるモル比で含む溶液と接触する。水酸化物イオン 対 スルフィドイオンの 高モル比により、スルフィド濃度の低い吸収溶液が生じる。白液または洗浄液の 様な吸収に使用されるアルカリ溶液は、約１３〜１４の高pH値を有するので、硫 化水素の吸収選択性が悪くなる。さらに、使用する吸収溶液は炭酸塩含有量が低 く、特に、炭酸塩含有量の高い緑液は洗浄液としては使用できないことが示され ている。 黒液蒸発、すなわち還元雰囲気中燃焼による黒液の蒸発、で使用する化学物質 を回収できる様にするため、およびこれらの化学物質からパルプ製造で使用する 白液を製造するためには、発生したガスから硫化水素を除去できることが必要で ある。ガスは二酸化炭素も含むので、二酸化炭素は液体吸収中に硫化水素と競合 し、また、ガスは硫化水素含有量が低く（約０．５％〜２％）、二酸化炭素含有 量が約２０倍高い（約１０〜２０％）ので、従来の液体吸収では、硫化水素の回 収が不十分である。 そのため、黒液の蒸発で発生し、硫化水素ならびに二酸化炭素を含むガスから 硫化水素を、高分離度および高度の選択性で分離する、と共に硫化水素を液体中 に、その中で高スルフィド含有量が得られる様に吸収させる方法が必要とされて いる。 本発明により、吸収媒体として炭酸塩含有アルカリ溶液を使用し、溶液のpHを 、新しい炭酸塩を加えることによってではなく、水酸化物を加えることによって 約９〜１２に調節する向流多段階吸収により、硫化水素の高度の分離ならびに硫 化水素の高度の選択性が達成されることが分かった。例えば、本発明により硫化 水素を６０〜７０％の選択性で吸収すると共に、硫化水素を約９０〜９９％の程 度で分離することができる。本発明によれば、流出する吸収溶液の総スルフィド 含有量は高い、すなわち約０．３０モル/lを超え、好ましくは約０．４７モル/l を超え、通常は約０．３０〜１．３０モル/lの範囲内、好ましくは約０．４７〜 １．１モル/lの範囲内、最も好ましくは約０．６５〜１．０モル/lの範囲内であ る。この溶液は硫酸塩パルプの製造における白液の製造に使用することができる 。 より詳しくは、本発明は、序文で述べた種類の、ガスが向流で、循環する炭酸 塩含有アルカリ溶液と多段階接触し、そのpHが吸収の際に水酸化物を加えること により約９〜１２に調節され、硫化水素が、流入ガスと接触する流出溶液中に総 スルフィド含有量が約０．３０モル/lを超えるまで吸収される方法を提供する。 本発明はさらに、序文で述べた種類の装置であって、ガスの入口およびガスの 出口を有する容器を含むこと、容器が、一連の連続する段階に配置された充填物 を含むこと、装置が、炭酸塩含有溶液を、ガスの供給方向で見て最後の段階に供 給する手段を有すること、各段階が、炭酸塩含有溶液を、その段階を通して向流 でガスに供給し、溶液をその段階に循環させる手段を有すること、装置が、溶液 の部分流を、ガスの供給方向で見て、ある段階からその前の段階に供給するため の導管を段階間に有していること、および装置が、炭酸塩含有溶液のpHを約９〜 １２に調節するためにこれらの段階の少なくとも一つにおいて水酸化物を溶液に 供給する手段、ならびに総スルフィド含有量が０．３０モル/lを超える液体を排 出するための、ガスの供給方向で見て最初の段階からの出口導管を有することを 特徴とする装置を提供する。 本発明の他の特徴は下記の説明および付随する請求項に記載する。 ここで使用する表現“炭酸塩含有アルカリ溶液”は、炭酸塩イオン（ＣＯ3 2- ）を含む水溶液を意味する。好ましくは、この溶液は、炭酸ナトリウム、炭酸カ リウムまたは炭酸リチウムの溶液の様なアルカリ金属炭酸塩溶液である。炭酸ナ トリウムが、容易に入手でき、かなり安価であるので、特に好ましい。溶液の炭 酸塩濃度は重要ではないが、炭酸塩に関して約０．１〜３Ｍが適当であり、好ま しくは約１〜２．５Ｍ、最も好ましくは約２Ｍである。 本発明では、炭酸塩含有アルカリ溶液のpHは少なくとも約９である。pH値が約 ９より低いと、硫化水素の吸収が不十分になり、すでに吸収された硫化水素が溶 液から放出される危険性さえある。しかし、溶液のpHは、高過ぎると二酸化炭素 の吸収と比較して硫化水素の吸収に悪影響を及ぼすので、あまり高くすべきでは ない。例えば、二酸化炭素の吸収があまりに著しくならない様に、溶液のpHは１ ２を超えるべきではない。好ましくは、溶液のpHは約１０．０〜１１．５、特 に約１０．０〜１１．０、最も好ましくは約１０．２〜１０．８である。溶液の pHをこの最後の狭い範囲内に調節すると、硫化水素の最適分離が達成される。 平衡反応（５）および（６）から分かる様に、炭酸水素イオン（ＨＣＯ3~）が 硫化水素および二酸化炭素の吸収の際に形成される。つまり、吸収溶液のpHは、 硫化水素および二酸化炭素の吸収が進むにつれて低下する。溶液のpHが約９より 下がると、硫化水素の吸収は不十分になり、前に述べた様に、すでに吸収された 硫化水素が溶液から放出される危険性さえある。これを避けるには、溶液を再生 する、すなわちそのPHを、問題とする温度およびpH値における気体状Ｈ2Ｓと液 体のスルフィド含有量間の平衡状態に対する許容下限より上に上げる必要がある 。しかし、pH値は、二酸化炭素の吸収が支配的となる約１２より高くしてはなら ない。本発明によりアルカリ金属水酸化物の様な水酸化物、例えばＮａＯＨ、を 加えることにより溶液のpH値を増加する結果、形成された炭酸水素塩イオンが、 下記の平衡反応により、炭酸塩イオンに再転化される。 この様に再生されることにより、炭酸塩溶液は上記の反応（５）により、より 多くの硫化水素を吸収することができる。溶液のpHは水酸化物の添加により調節 され、約９〜１２、好ましくは約１０．０〜１１．５、特に約１０．０〜１１． ０、最も好ましくは約１０．２〜１０．８の特定範囲内に維持されるので、二酸 化炭素の吸収は無視できる程の低水準に維持される。 上記の様に、炭酸塩含有アルカリ溶液は水酸化物を加えることにより再生され る。基本的に、硫化水素の吸収に悪影響を及ぼさず、溶液のpHを約９の下限から 、約１２．０を超えない、好ましくは約１１．５を超えない、最も好ましくは約 １０．８を超えない値の様な、所望の値に増加させることができる、すべての水 酸化物を使用することができる。本発明により、水酸化ナトリウム（ＮａＯＨ） 、水酸化カリウム（ＫＯＨ）、水酸化リチウム（ＬｉＯＨ）、水酸化カルシウム （Ｃａ（ＯＨ）2）および水酸化マグネシウム（Ｍｇ（ＯＨ）2）の様な、アルカ リ金属またはアルカリ土類金属の水酸化物を使用するのが好ましい。入手性およ び原価から、水酸化ナトリウムが最も好ましい。 本発明の吸収に使用する液体の温度は特に重要ではなく、広い範囲内で変える ことができるが、硫化水素の吸収は約８０℃以上の温度で低下するという危険性 があるので、好ましくは約８０℃未満にすべきである。温度は好ましくは室温、 すなわち約２０℃から約８０℃迄、より好ましくは約４０〜７０℃、特に約５０ 〜７０℃、最も好ましくは約６０〜７０℃である。 本発明によれば、液体吸収における硫化水素の選択性は、ガスの流れと吸収液 体の流れが向流になる様に吸収を行ない、ガスを乱流にし、液体を層流にするこ とにより、最適化される。さらに、硫化水素の分離は、硫化水素が吸収されるガ スの体積に比べて吸収液体の体積が大きい場合に促進される。液体 対 気体の その様な高比率は、硫化水素含有ガスと接触する吸収液体を循環させることによ り得られる。 その上、硫化水素含有ガスと吸収液体（炭酸塩含有溶液）の接触には幾つかの 段階、好ましくは２または３段階、最も好ましくは３段階が関与する。その様な 多段階接触では、個々の段階における時間が短縮されるので炭酸塩含有溶液のpH が約９より下に落ちる時間がなく、同時にスルフィド含有量が最も上の段階にお いても低く維持される。好ましくは、各段階は、その段階の末端における溶液の pHが約１０．０〜１０．２に低下する様な大きさ、または長さを有し、次いで液 体は取り出され、水酸化物で再生され、その段階に再循環される。 ここで、本発明の装置の好ましい実施態様を示す添付の図面を参照しながら本 発明を説明する。 本発明の装置は、黒液蒸発で発生した、硫化水素ならびに二酸化炭素を含むガ ス３の入り口２を有する塔または容器１を含む。装置の反対側の末端には、液体 吸収により硫化水素が除去されたガス５の出口がある。硫化水素含有ガスと炭酸 塩含有溶液の接触には３つの段階６、７および８が関与する。各段階は、図面の 段階６で示す充填物９を含む。吸収の際の硫化水素の選択性を最適化するために 、充填物９は、段階６、７および８を通して液体の層流が発生する様な形状を有 する。本発明により、波形板の形態の充填物がこの目的に特に好適であることが 分かった。例えば、充填物はプラスチックまたは金属で製造することができる。 硫化水素を吸収する炭酸塩含有溶液と硫化水素含有ガスの接触は、向流様式で 行なわれる。このために、各段階は、炭酸塩含有溶液をその段階を通して、ガス に対して向流になる様に供給する手段、ならびにその段階に溶液を循環させる手 段を有する。図に示す様に、これらの手段は、導管１３、１４および１５を経由 して炭酸塩含有アルカリ溶液をそれぞれの段階６、７および８に供給するポンプ １０、１１および１２、ならびにそれぞれの段階から溶液を収集容器１９、２０ および２１に導く導管１６、１７および１８からなる。これらの収集容器から溶 液は、それぞれポンプ１０、１１および１２に接続された導管２２、２３および ２４を通して各段階に循環される。新しい炭酸塩溶液、好ましくは炭酸ナトリウ ム溶液、が炭酸ナトリウム溶液の供給源（図には示していない）から導管２５を 通して、供給方向で見て最後の段階６に供給される。 最後の段階に新しい炭酸塩溶液を供給する代わりに、最後の段階に水酸化ナト リウム溶液を供給し、上記の反応（３）〜（４）により炭酸塩含有溶液が得られ る様に、水酸化物溶液にガスから二酸化炭素を吸収させることにより、炭酸塩溶 液を最後の段階で発生させることもできる。 吸収溶液のpHを調節（増加）するために、水酸化物、好ましくは水酸化ナトリ ウム溶液を収集容器１９、２０および２１に、それぞれ、すべての導管に対して 共通の供給源（図には示していない）からアルカリを導入する導管２６、２７お よび２８を通して供給することができる。吸収溶液のpHを調節するための水酸化 ナトリウム溶液の供給は、収集容器１９、２０および２１中の溶液の測定pH値に 基づいて調整する（図には示していない）。 図面から分かる様に、各段階はさらに導管２９および３０により相互に接続さ れており、吸収溶液の部分流をある段階からその前の段階へ、すなわち段階６か ら段階７へ、ならびに段階７から段階８へ供給する。 最後に、収集容器２１および段階８からスルフィド含有液体を排出するために 、出口導管３１が配置されている。 本発明を非限定的な実施例によりさらに説明する。実施例１ 黒液蒸発で発生したガスから硫化水素を選択的に除去する試験を行なった。上 に説明した、添付の図面に示す種類の装置を使用した。 吸収は大気圧で行ない、流入ガスは、温度が約６０℃で、１．１３モル％の硫 化水素および１６．９モル％の二酸化炭素を含んでいた。ガスを上記の温度で、 約１８．７モル％の水に相当する水蒸気で飽和させた。流入するガス流量は３８ ，２８０Nm3/hで、吸収塔内のガス速度は約３．１m/sであった。吸収塔は高さが ６．２５ｍであり、最初の２段階はそれぞれ高さが１．５ｍであり、ガスの供給 方向で見て最後の段階は高さが１ｍであった。各段階には、Sulzer製のMellapac k 500型の充填物を入れた。塔の直径は２．３mであった。 ８．８m3/hの２Ｍ炭酸ナトリウム溶液からなる、温度約６０℃の新しい吸収溶 液を、循環する吸収溶液と共に、塔の最後の段階に、合計約５０m3/hの吸収溶液 が塔の最後の段階に供給される様に供給した。供給する吸収溶液のpHは約１１． ０であったが、これは、溶液がその段階を通過する際に硫化水素の吸収により約 １０．２に低下した。この段階を通過した後、溶液は１．５m3の収集容器に集め 、そこで溶液を、２．５Ｍの、温度約６０℃の水酸化ナトリウム溶液を加え、溶 液のpHが再び約１１．０に増加する様にして再生した。次いで、再生さ れた溶液をポンプにより吸収塔の最後の段階に循環させ、新たに硫化水素を吸収 させた。 最後の段階の収集容器から約１１m3/hの吸収溶液を中間段階の収集容器に取り 出し、そこから５０m3/hの、pH約１１．０の吸収溶液を前の段階と同様に中間段 階にポンプ輸送し、そこから、pH約１０．２の吸収溶液を取り出して収集容器に 循環した。収集容器中で、前の段階と同様に、温度約６０℃の２．５Ｍ水酸化ナ トリウム溶液を加えて溶液を再生した。 中間段階の収集容器から約１３．５m3/hの吸収溶液を第一（最も下の）段階の 収集容器に取り出し、そこから５０m3/hの、pH約１１．０の吸収溶液を、ガスの 供給方向で見て第一段階にポンプ輸送した。この段階を通過し、そこで硫化水素 を吸収した後、この時点でpH約１０．２を有する溶液を収集容器に取り出した。 この収集容器中で、前の段階と同様に、温度約６０℃の２．５Ｍ水酸化ナトリウ ム溶液を加え、再生された溶液のpHが約１１．０になる様に溶液を再生した。全 体的に見て、約８．６m3/hの２．５Ｍ水酸化ナトリウム溶液が３段階の収集容器 に供給された。 第一（最も下の）段階の収集容器から、スルフィド濃度１モル/lを有する溶液 約１７．４m3/hが取り出された。吸収塔から出るガスは０．１１３モル％の硫化 水素および１６．４モル％の二酸化炭素を含んでいた。この試験では、硫化水素 の分離程度は約９０％であり、分離における硫化水素の選択性は約６７％であつ た。 本発明による吸収を行なった溶液は、スルフィド含有量が高く、アルカリ金属 炭酸塩含有量が高いので、硫酸塩パルプの製造に使用する白液の製造に非常に適 している。本発明により、硫化水素を吸収した後に吸収塔を離れる溶液は、上記 の様に、スルフィド含有量が約０．３０モル/lを超え、好ましくは約０．４７モ ル/lを超えている。通常、スルフィド含有量は約０．３０〜１．３０モル/lの範 囲、好ましくは約０．４７〜１．１モル/lの範囲、最も好ましくは約０．６５〜 １．０モル/lの範囲内にある。上記の様に、炭酸塩含有量は約０．１〜３Ｍ、好 ましくは約１〜２．５Ｍ、最も好ましくは約２Ｍである。Detailed Description of the Invention Method and apparatus for absorbing hydrogen sulfide The present invention relates to a method and apparatus for absorbing hydrogen sulfide, and more particularly, a liquid in black liquor evaporation. Absorption selectively removes hydrogen sulfide from gases containing hydrogen sulfide and carbon dioxide A method and device for leaving. Hydrogen sulfide is mainly hydrogen sulfide ion (HS-) Is absorbed in the form of Fido ion (S2-) Is also absorbed. Below, the total content of these ions Is collectively referred to as "total sulfide content" or shorter "sulfide content" . Hydrogen sulfide is absorbed by an aqueous alkaline solution such as sodium hydroxide. , Or ethanolamines such as monoethanolamine and diethanol It is well known that the use of amines can remove hydrogen sulfide-containing gases. Have been. This absorption method is used, for example, for the production of hydrogen sulfide in pure form, and If desired, it can be used further for treating sulfur in the Claus process. gas If carbon dioxide contains carbon dioxide in addition to hydrogen sulfide, the carbon dioxide will also be absorbed by the alkaline solution. Will be collected. The solubility of carbon dioxide in water is almost the same as that of hydrogen sulfide, Therefore, carbon dioxide competes with hydrogen sulfide and is absorbed in the solution. Hydrogen sulfide and dioxide Carbon is absorbed by an alkaline aqueous solution of sodium hydroxide according to the following formula. To be done. H2S + OH- → HS-+ H2O (1) H2S + 2OH- → S2-+ 2H2O (2) CO2+ OH- → HCO3 - (3) CO2+ 2OH- → CO3 2-+ H2O (4) Selectivity for hydrogen sulfide, ie the number of moles of hydrogen sulfide absorbed and absorbed The ratio of the number of moles of (hydrogen sulfide + carbon dioxide) is the hydrogen sulfide and carbon dioxide of the gas. It is directly proportional to the elemental content. Therefore, most of the competition for carbon dioxide is Especially when the gas contains more carbon dioxide than hydrogen sulphide. Is remarkable. The gas is, for example, 1% by volume hydrogen sulfide and 10% by volume carbon dioxide. When you try to absorb hydrogen sulfide with sodium hydroxide solution, The selectivity is only 10%, ie 90% of the gas absorbed is carbon dioxide 90% of the sodium hydroxide is spent on the absorption of carbon dioxide. The above-mentioned problems when absorbing hydrogen sulfide from gases containing hydrogen sulfide and carbon dioxide. To improve convenience, methods have been developed to selectively absorb hydrogen sulfide. An example For example, strong acids such as potassium permanganate, sodium dichromate or ferric salts. Efforts have been made to selectively absorb hydrogen sulfide into a solution of the agent. Other alternatives The method uses an alkaline solution such as sodium carbonate or potassium carbonate to absorb The operating conditions in are carefully adjusted. More detailed information about this prior art The report is C.I. Oloman, F.E. Murray and J.B. Risk “Sulfide water from flue gas Article entitled "Selective Absorption of Elements," Pulp and Paper Magazine of Canada, 196. December 5, 1997, pages 69 et seq. Bendall, R.C. Aiken and F. Manda “A large amount of CO due to absorption and reaction in micro-spray2H from2Of S Article entitled "Selective Absorption", AICHE Journal (Vol.29, No, 1), 1983, 1 Months, starting on page 66. One example of the prior art is, for example, a method of recovering sulfur from furnace gas generated by combustion of black liquor. The method is described in US-3,554,859. Hydrogen sulfide and dioxide Combustion gas containing carbon is mixed with gas containing molecular oxygen and, for example, sodium hydroxide. Form of um and sodium carbonate or sodium carbonate and sodium hydrogen carbonate Contact with an alkaline aqueous solution containing a sodium ion in a solid state. Thus, hydrogen sulfide It is absorbed from the gas and oxidized to thiosulfate. This absorption is due to the addition of ferric oxide It is even more effective, thus maintaining the sulfide concentration of the solution at a very low level. Retained, ie the sulfide concentration of the solution is minimized. Instead of a hydroxide solution, such as sodium hydroxide solution, The absorption selectivity of hydrogen sulfide is about 30-50% by using such carbonate solution. Increase. The reaction that takes place upon such absorption is generally described as follows. If the absorbing solution is a carbonate solution, hydrogen sulfide will be absorbed almost instantaneously. On the other hand, carbon dioxide reacts very slowly with carbonate ions, and Form When using a carbonate solution as the absorption medium, a high concentration of bicarbonate As is clear from the above equilibrium equation (6), Further advantages of "counter pressure" (equilibrium pressure) are obtained. The problem that arises when using a carbonate solution as the absorption medium is the bicarbonate ion Due to the reduced absorption capacity caused by the formation of It means that only the desired content is achieved. Therefore, about 0.30 mol / l It is extremely difficult to obtain a sulfide content above. As a result, carbonate solution Prior art methods for selectively absorbing hydrogen sulfide using absorption media in the form of In many areas where hydrogen-containing and carbon dioxide-containing gases are generated, such methods are suitable. Despite the great demand for it, it hasn't achieved much. Such response Examples of fields of use are oil refining, coal gas production, and especially in the sulphate pulp industry. It is the burning of black liquor. When recovering chemicals in the sulfate industry by the conventional Tomlinson method, black liquor is It is burned in a feeder recovery device to generate steam, which mainly contains sodium carbonate and sulfide. A melt consisting of sodium is formed. The melt is then dissolved in water and causticized , Converting sodium carbonate to sodium hydroxide gives white liquor, which is a wood Can be reused for digestion. Explosion hazard when the soda recovery device tube ruptures In recent years, black liquor is thermally decomposed under reducing conditions for many reasons including Efforts are being made to develop new methods for the burning of black liquor, in which no black matrix is formed. Such a method is generally called "black liquor evaporation", and one example is the so-called SCA-Bi. llerud method (E. Horntvedt and J. Gomy, Paper Trade Journal 158 (1974) 16, pages 32 to 34). In this method, the black liquor in the reactor is mainly sodium carbonate. Formation of combustible gas containing dust and especially sulfur compounds consisting of aluminum and carbon Thermal decomposition is carried out under such temperature conditions. Another example of black liquor evaporation is the stoichiometrically required amount. At a pressure of more than 10 bar, the melt is shaped US Pat. No. 4,872,95 on a method of thermally decomposing black liquor at a temperature such that it is not formed 0 is disclosed. By evaporation, a solid phase consisting mainly of sodium carbonate, And primarily hydrogen sulfide, carbon monoxide, carbon dioxide, hydrogen, water vapor, and methane A gas phase consisting of is formed. EP 459,962 relates to the purification of process gases in black liquor evaporation. This pure In the conversion, contact with an alkaline solution containing hydrogen sulfide and hydroxide ions This removes sulfur compounds and sodium compounds from the gas. For purification Involves at least two steps. In the first step, the gas together with the alkaline solution After passing through the Venturi nozzle, the molten aerosol droplets of black liquor in the gas are Be absorbed. The gas is then 4: 1 with hydroxide ions and hydrogen sulfide ions. Contact with a solution containing it in a molar ratio exceeding. Of hydroxide ion vs. sulfide ion The high molar ratio results in an absorbent solution with low sulfide concentration. Of white or cleaning liquid Since the alkaline solution used for such absorption has a high pH value of about 13-14, Absorption selectivity of hydrogen fluoride deteriorates. In addition, the absorbent solution used has a low carbonate content. In particular, it has been shown that green liquor with a high carbonate content cannot be used as a cleaning solution. ing. Chemicals used in black liquor evaporation, i.e. black liquor evaporation due to combustion in a reducing atmosphere To be recovered and used in pulp production from these chemicals In order to produce white liquor, it is necessary to be able to remove hydrogen sulfide from the generated gas. is there. Since gas also contains carbon dioxide, carbon dioxide competes with hydrogen sulfide during liquid absorption. In addition, the gas has a low hydrogen sulfide content (about 0.5% to 2%) and contains carbon dioxide. Since the amount is about 20 times higher (about 10 to 20%), the conventional liquid absorption is less than that of hydrogen sulfide. The income is insufficient. Therefore, it is generated by the evaporation of black liquor, and from gas containing hydrogen sulfide and carbon dioxide. Separation of hydrogen sulfide with high resolution and high selectivity, and hydrogen sulfide in liquid In addition, there is a need for a method of absorption so that a high sulfide content can be obtained. There is. According to the invention, a carbonate-containing alkaline solution is used as the absorption medium and the pH of the solution is , Not by adding new carbonate, but by adding hydroxide Countercurrent multi-stage absorption adjusted to about 9-12 provides a high degree of separation and sulfurization of hydrogen sulfide. It has been found that a high degree of selectivity of hydrogen fluoride is achieved. For example, according to the invention It absorbs hydrogen with a selectivity of 60-70%, and about 90-99% of hydrogen sulfide. Can be separated in degrees. According to the invention, the total sulphide of the absorbing solution flowing out High content, ie greater than about 0.30 mol / l, preferably about 0.47 mol / l , Usually in the range of about 0.30 to 1.30 mol / l, preferably about 0.47 to Within the range of 1.1 mol / l, most preferably within the range of about 0.65-1.0 mol / l. It This solution can be used for the production of white liquor in the production of sulfate pulp . More particularly, the present invention relates to a gas countercurrent, circulating carbonic acid of the type mentioned in the introduction. Multi-step contact with a salt-containing alkaline solution, adding hydroxide when its pH is absorbed Adjusted to approximately 9-12 by the total hydrogen sulfide in the effluent solution in contact with the incoming gas. A method is provided wherein the sulfide content is absorbed up to greater than about 0.30 mol / l. The invention further comprises a device of the type mentioned in the preamble, wherein the gas inlet and the gas Including a container having an outlet, the container wherein the container is arranged in a series of successive stages The device is adapted to provide the carbonate-containing solution to the last stage as viewed in the gas feed direction. Each step has a means for feeding a carbonate-containing solution countercurrent through the step. Having means for supplying gas to the solution at the stage and circulating the solution at that stage To supply the partial flow of the gas from one stage to the previous stage when viewed in the gas supply direction. Between the stages, and the apparatus has a pH of the carbonate-containing solution of about 9 to In at least one of these steps the hydroxide is brought into solution in order to adjust Means for supplying and discharging liquid with a total sulfide content exceeding 0.30 mol / l To have an outlet conduit from the first stage, viewed in the gas feed direction, A characteristic device is provided. Other features of the invention are set forth in the following description and the appended claims. As used herein, the expression "carbonate-containing alkaline solution" refers to carbonate ion (CO3 2- ) Is included. Preferably, this solution is sodium carbonate, An alkali metal carbonate solution, such as a solution of lithium or lithium carbonate. Carbonated Thorium is particularly preferred because it is readily available and fairly inexpensive. Solution charcoal The acid salt concentration is not critical, but about 0.1 to 3 M is suitable for carbonate and is preferred. It is preferably about 1 to 2.5M, most preferably about 2M. In the present invention, the pH of the carbonate-containing alkaline solution is at least about 9. pH value is approx. If it is lower than 9, the absorption of hydrogen sulfide will be insufficient and the already absorbed hydrogen sulfide will dissolve. There is even a risk of being released from the liquid. However, if the pH of the solution is too high, carbon dioxide will Should not be too high, as it has a negative effect on the absorption of hydrogen sulfide compared to the absorption of Absent. For example, the pH of the solution should be 1 so that the absorption of carbon dioxide is not too significant. Should not exceed 2. Preferably, the pH of the solution is about 10.0-11.5, Is about 10.0 to 11.0, most preferably about 10.2 to 10.8. Of solution Adjusting the pH within this last narrow range achieves optimum separation of hydrogen sulfide. As can be seen from the equilibrium reactions (5) and (6), bicarbonate ion (HCO3~) Is It is formed upon absorption of hydrogen sulfide and carbon dioxide. That is, the pH of the absorbing solution is It decreases as the absorption of hydrogen sulfide and carbon dioxide progresses. The pH of the solution is about 9 When it goes down, the absorption of hydrogen sulfide becomes inadequate, and as already mentioned, it has already been absorbed. There is even a risk of hydrogen sulfide being released from the solution. To avoid this, regenerate the solution I.e., its PH is changed to gaseous H at the temperature and pH value in question.2S and liquid Must rise above the lower tolerance limit for equilibrium between body sulfide contents . However, the pH should not be higher than about 12 where carbon dioxide absorption is dominant. Absent. According to the invention, a hydroxide such as an alkali metal hydroxide, for example NaOH, As a result of increasing the pH value of the solution by adding, the bicarbonate ions formed are It is reconverted to carbonate ion by the following equilibrium reaction. By being regenerated in this way, the carbonate solution can be further treated by the above reaction (5). It can absorb a large amount of hydrogen sulfide. Adjust the pH of the solution by adding hydroxide About 9-12, preferably about 10.0-11.5, especially about 10.0-11. 0, most preferably within a specified range of about 10.2-10.8, so that the diacid Carbon dioxide absorption is maintained at a negligibly low level. As mentioned above, the carbonate-containing alkaline solution is regenerated by adding hydroxide. It Basically, it does not adversely affect the absorption of hydrogen sulfide and keeps the pH of the solution from the lower limit of about 9. , Not more than about 12.0, preferably not more than about 11.5, most preferably about Any water that can be increased to a desired value, such as a value not exceeding 10.8 Oxides can be used. According to the present invention, sodium hydroxide (NaOH) , Potassium hydroxide (KOH), lithium hydroxide (LiOH), calcium hydroxide (Ca (OH)2) And magnesium hydroxide (Mg (OH))2), Arca Preference is given to using hydroxides of metal or alkaline earth metals. Availability and Sodium hydroxide is most preferred because of its low cost. The temperature of the liquid used for absorption according to the invention is not particularly critical and can be varied within wide limits. However, there is a risk that absorption of hydrogen sulfide will decrease at temperatures above about 80 ° C. Therefore, it should preferably be below about 80 ° C. The temperature is preferably room temperature, That is, from about 20 ° C to about 80 ° C, more preferably about 40-70 ° C, especially about 50 ° C. ~ 70 ° C, most preferably about 60-70 ° C. According to the present invention, the selectivity of hydrogen sulfide in liquid absorption depends on the gas flow and the absorption liquid. It absorbs so that the body flow is countercurrent, making the gas turbulent and the liquid laminar. Optimized by and. Furthermore, the separation of hydrogen sulfide is a It is promoted when the volume of the absorbing liquid is larger than the volume of the liquid. Liquid vs. gas Such a high ratio is due to the circulation of the absorbing liquid in contact with the hydrogen sulfide-containing gas. Can be obtained. Moreover, contact between the hydrogen sulfide-containing gas and the absorbing liquid (carbonate-containing solution) requires several Stages are involved, preferably 2 or 3 stages, most preferably 3 stages. Like that In multi-step contact, the pH of the carbonate-containing solution is Has no time to fall below about 9 and at the same time the sulfide content is at the highest stage. Even if it is kept low. Preferably, each step comprises a solution at the end of that step. It has a size or length such that the pH drops to about 10.0-10.2, and then the liquid The body is removed, regenerated with hydroxide and recycled to that stage. Reference will now be made to the accompanying drawings which illustrate preferred embodiments of the apparatus of the present invention. The invention will be described. The apparatus of the present invention includes a gas containing hydrogen sulfide and carbon dioxide generated by black liquor evaporation. It comprises a tower or vessel 1 with an inlet 2 for a gas 3. Liquid on the other end of the device There is an outlet for gas 5 from which hydrogen sulfide has been removed by absorption. Hydrogen sulfide-containing gas and carbonic acid Contacting the salt-containing solution involves three stages 6, 7 and 8. Each stage of the drawing Includes fill 9 shown in step 6. To optimize the selectivity of hydrogen sulfide for absorption , The packing 9 has a shape such that a laminar flow of liquid occurs through steps 6, 7 and 8. To do. According to the invention, fillings in the form of corrugated plates are particularly suitable for this purpose. Do you get it. For example, the filling can be made of plastic or metal. The contact between the carbonate-containing solution that absorbs hydrogen sulfide and the hydrogen sulfide-containing gas is countercurrent. Done. To this end, each step involves passing a carbonate-containing solution through the gas phase. A means for supplying a countercurrent to the liquid, and a means for circulating the solution at that stage. With steps. As shown, these means are via conduits 13, 14 and 15. Pump to supply the carbonate-containing alkaline solution to each stage 6, 7 and 8 Solution collection vessels 19, 20 from 10, 11 and 12 and their respective stages And conduits 16, 17 and 18 leading to 21. Melt from these collection vessels The liquid is supplied to conduits 22, 23 and 23 connected to pumps 10, 11 and 12, respectively. It is cycled through 24 to each stage. Fresh carbonate solution, preferably sodium carbonate Solution from the source of sodium carbonate solution (not shown) through conduit 25. Through the final stage 6 as seen in the feed direction. Instead of feeding fresh carbonate solution to the last step, the last step A solution containing a carbonate is supplied, and a carbonate-containing solution is obtained by the above reactions (3) to (4). As described above, the carbonate solution is absorbed by absorbing carbon dioxide from the gas in the hydroxide solution. It is also possible to generate the liquid in the final stage. To adjust (increase) the pH of the absorption solution, a hydroxide, preferably sodium hydroxide Umium solution into collection vessels 19, 20 and 21 respectively for all conduits The conduits 26, 27 for introducing alkali from a common source (not shown) And 28. Hydroxylation to adjust the pH of the absorption solution The supply of sodium solution depends on the measured pH value of the solution in the collecting vessels 19, 20 and 21. Adjust based on (not shown). As can be seen from the drawing, the stages are further interconnected by conduits 29 and 30. The partial flow of the absorbing solution from one stage to the preceding stage, ie To stage 7 and from stage 7 to stage 8. Finally, to drain the sulphide-containing liquid from the collection vessel 21 and step 8. An outlet conduit 31 is arranged. The invention will be further described by means of non-limiting examples.Example 1 A test was conducted to selectively remove hydrogen sulfide from the gas generated by black liquor evaporation. Up An apparatus of the type illustrated in the accompanying drawings and described in Section 1 was used. Absorption is carried out at atmospheric pressure and the inflowing gas has a temperature of about 60 ° C. and a sulfur content of 1.13 mol%. It contained hydrogen fluoride and 16.9 mol% carbon dioxide. The gas at the above temperature, It was saturated with steam corresponding to about 18.7 mol% of water. Inflow gas flow rate is 38 280Nm3/ h, the gas velocity in the absorber was about 3.1 m / s. The height of the absorption tower 6.25m, the first two stages are each 1.5m high, gas supply The final stage, viewed in direction, was 1 m high. Each stage has a Sulzer-made Mellapac A k500 type charge was placed. The tower diameter was 2.3 m. 8.8m3A new absorption solution consisting of 2M sodium carbonate solution of 60 / h at a temperature of about 60 ℃. The liquid, together with the circulating absorption solution, is added to the last stage of the tower for a total of about 50 m.3/ h absorption solution Was fed to the last stage of the tower. The pH of the absorption solution supplied is about 11. It was 0, which was due to absorption of hydrogen sulfide as the solution passed through the stage. It dropped to 10.2. After passing this stage, the solution is 1.5m3Collect in a collection container , So that the solution is dissolved by adding 2.5M sodium hydroxide solution at a temperature of about 60 ° C. The solution was regenerated so that the pH of the solution increased again to about 11.0. Then played The pumped solution is circulated to the last stage of the absorption tower by a pump to absorb new hydrogen sulfide. Let Approximately 11m from the last stage collection container3/ h absorption solution into an intermediate stage collection container Out, 50m from there3/ h, absorption solution of pH about 11.0, as in the previous step Pump to the floor, from which the absorption solution with a pH of about 10.2 is taken and placed in a collection container. Circulated. In a collection vessel, as in the previous step, 2.5M sodium hydroxide at a temperature of about 60 ° C. Thorium solution was added to regenerate the solution. Approximately 13.5m from the intermediate stage collection container3/ h absorption solution for the first (bottom) stage 50m from there3/ h, absorption solution of pH about 11.0, Pumped to the first stage as viewed in the feed direction. Pass this stage, where hydrogen sulfide At this point, the solution having a pH of about 10.2 was removed into a collection vessel after the absorption of. In this collecting vessel, as in the previous step, 2.5M sodium hydroxide with a temperature of about 60 ° C was used. Solution was added and the solution was regenerated so that the pH of the regenerated solution was about 11.0. all Physically, about 8.6m3/ h 2.5M sodium hydroxide solution is a three-stage collection container Was supplied to. Solution with a sulphide concentration of 1 mol / l from the first (bottom) stage collection vessel About 17.4m3/ h was taken out. The gas from the absorption tower is 0.113 mol% sulfurized It contained hydrogen and 16.4 mol% carbon dioxide. In this test, hydrogen sulfide The separation degree is about 90%, and the selectivity of hydrogen sulfide in the separation is about 67%. It was The solution absorbed according to the present invention has a high sulfide content and Its high carbonate content makes it very suitable for the production of white liquor used in the production of sulfate pulp. are doing. According to the invention, the solution leaving the absorption tower after absorbing hydrogen sulfide is The sulfide content exceeds about 0.30 mol / l, preferably about 0.47 mol / l. Le / l is exceeded. Usually, the sulfide content is in the range of about 0.30 to 1.30 mol / l. Range, preferably in the range of about 0.47 to 1.1 mol / l, most preferably about 0.65. It is in the range of 1.0 mol / l. As mentioned above, the carbonate content is about 0.1-3M, It is preferably about 1 to 2.5M, most preferably about 2M.
【手続補正書】特許法第１８４条の８ 【提出日】１９９５年３月６日 【補正内容】 請求の範囲 １． 黒液蒸発において発生した硫化水素ならびに二酸化炭素を含むガス（３ ）から、液体吸収により硫化水素を選択的に除去する方法であって、ガス（３） が向流で、循環する炭酸塩含有アルカリ溶液（１３、１４、１５）と多段階接触 （６、７、８）し、溶液のpHが、水酸化物（２６、２７、２８）を加えることに より各段階における吸収の際に約９〜１２に調節され、硫化水素が、硫化水素イ オンおよびスルフィドイオンとして、流入ガスと接触した流出溶液中に総スルフ ィド含有量が約０．３０モル/lを超えるまで吸収されることを特徴とする方法。 ２． アルカリ金属水酸化物、好ましくは水酸化ナトリウム、が加えられるこ とを特徴とする、請求項１に記載の方法。 ３． pHが約１０〜１１．５に調節されることを特徴とする、請求項１または ２に記載の方法。 ４． 硫化水素が、流出溶液中のスルフィド含有量が約０．４７〜１．１モル /lになるまで吸収されることを特徴とする、請求項１〜３のいずれか１項に記載 の方法。 ５． 炭酸塩含有アルカリ溶液の炭酸塩含有量が約０．１〜３Ｍであることを 特徴とする、請求項１〜４のいずれか１項に記載の方法。 ６． ガスが炭酸ナトリウム溶液と接触することを特徴とする、請求項１〜５ のいずれか１項に記載の方法。 ７． ガスが３段階（６、７、８）で溶液と接触することを特徴とする、請求 項１〜６のいずれか１項に記載の方法。 ８． ガスおよび溶液が液体層流とガス乱流の条件下で接触することを特徴と する、請求項１〜７のいずれか１項に記載の方法。 ９． 黒液蒸発において発生した硫化水素ならびに二酸化炭素を含むガス（３ ） から、液体吸収により硫化水素を選択的に除去するために使用する装置であって 、装置がガスの入口（２）およびガスの出口（４）を有する容器（１）を含むこ と、容器（１）が一連の段階（６、７、８）に配置された充填物（９）を含むこ と、装置が、炭酸塩含有溶液を、ガスの供給方向で見て最後の段階に供給する手 段（２５）を有すること、各段階が、炭酸塩含有溶液を、その段階を通して向流 でガスに供給し、溶液をその段階に循環させる手段を有すること、装置が、溶液 の部分流を、ガスの供給方向で見てある段階からその前の段階に供給するための 導管（２９、３０）を段階間に有していること、および装置が、各段階における 炭酸塩含有溶液のpHを約９〜１２に調節するために水酸化物を炭酸塩含有溶液に 供給する手段（２６、２７、２８）、ならびに硫化水素イオンおよびスルフィド イオンとして吸収された硫化水素を約０．３０モル/lを超える総スルフィド含有 量で含む液体を排出するための、ガスの供給方向で見て最初の段階からの出口導 管（３１）を有することを特徴とする装置。 １０． 三つの段階を有し、充填物（９）が波形板の形態であることを特徴と する、請求項９に記載の装置。[Procedure Amendment] Patent Act Article 184-8 [Submission date] March 6, 1995 [Correction content] The scope of the claims 1. Gas containing hydrogen sulfide and carbon dioxide (3 ), A method for selectively removing hydrogen sulfide by liquid absorption, comprising: Countercurrent, multi-step contact with circulating carbonate-containing alkaline solution (13, 14, 15) (6,7,8) and the pH of the solution depends on the addition of hydroxide (26,27,28). It is adjusted to about 9 to 12 during absorption at each stage, and hydrogen sulfide is adjusted to As total on- and sulphide ions, total sulfur is present in the effluent solution in contact with the incoming gas. The method is characterized in that the metal oxide content is absorbed until it exceeds about 0.30 mol / l. 2. Alkali metal hydroxide, preferably sodium hydroxide, is added. The method according to claim 1, characterized by: 3. The pH is adjusted to about 10 to 11.5, or The method described in 2. 4. Hydrogen sulfide has a sulfide content of about 0.47 to 1.1 mol in the effluent solution. 4. Absorption up to / l, 4. Any one of claims 1 to 3, characterized in that the method of. 5. The carbonate content of the carbonate-containing alkaline solution should be about 0.1-3M. Method according to any one of claims 1 to 4, characterized. 6. Gas is in contact with a sodium carbonate solution. The method according to any one of 1. 7. The gas is contacted with the solution in three steps (6, 7, 8), Item 7. The method according to any one of Items 1 to 6. 8. Characterized in that the gas and the solution come into contact with each other under the conditions of laminar gas flow and turbulent gas flow. The method according to claim 1, wherein 9. Gas containing hydrogen sulfide and carbon dioxide (3 ) Is a device used to selectively remove hydrogen sulfide by liquid absorption. The device comprises a container (1) having a gas inlet (2) and a gas outlet (4). And the container (1) contains a filling (9) arranged in a series of stages (6, 7, 8). And the device supplies the carbonate-containing solution to the last stage as viewed in the gas supply direction. Having stages (25), each stage allowing a carbonate-containing solution to flow countercurrently through the stages Having means for supplying gas to the solution at the stage and circulating the solution at that stage To supply the partial flow of the gas from one stage to the preceding stage in the gas supply direction. Having conduits (29, 30) between stages, and the device at each stage Hydroxide was added to the carbonate-containing solution to adjust the pH of the carbonate-containing solution to about 9-12. Means for supplying (26, 27, 28), and hydrogen sulfide ions and sulfides Total sulfide content exceeds about 0.30 mol / l of hydrogen sulfide absorbed as ions The outlet guide from the first stage in the direction of gas supply for discharging the liquid containing in volume. Device having a tube (31). 10. Characterized in that it has three stages, the filling (9) being in the form of a corrugated plate The device of claim 9, wherein
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ Ｄ２１Ｃ 11/12 7199−3Ｂ (81)指定国 ＥＰ(ＡＴ，ＢＥ，ＣＨ，ＤＥ， ＤＫ，ＥＳ，ＦＲ，ＧＢ，ＧＲ，ＩＥ，ＩＴ，ＬＵ，Ｍ Ｃ，ＮＬ，ＰＴ，ＳＥ)，ＯＡ(ＢＦ，ＢＪ，ＣＦ，ＣＧ ，ＣＩ，ＣＭ，ＧＡ，ＧＮ，ＭＬ，ＭＲ，ＮＥ，ＳＮ， ＴＤ，ＴＧ)，ＡＴ，ＡＵ，ＢＢ，ＢＧ，ＢＲ，ＢＹ， ＣＡ，ＣＨ，ＣＮ，ＣＺ，ＤＥ，ＤＫ，ＥＳ，ＦＩ，Ｇ Ｂ，ＨＵ，ＪＰ，ＫＰ，ＫＲ，ＫＺ，ＬＫ，ＬＵ，ＬＶ ，ＭＧ，ＭＮ，ＭＷ，ＮＬ，ＮＯ，ＮＺ，ＰＬ，ＰＴ， ＲＯ，ＲＵ，ＳＤ，ＳＥ，ＳＫ，ＵＡ，ＵＳ，ＵＺ，Ｖ Ｎ (72)発明者 ベングトソン，スネ スエーデン国ベクシェ、ビッカーベーゲ ン、16 (72)発明者 ダールクビスト，エリック スエーデン国ベステロス、グドルンス、ベ ーク、51 【要約の続き】 ルフィド含有液体を排出するための、ガスの供給方向で 見て最初の段階からの出口導管（３１）を有する。─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Internal reference number FI D21C 11/12 7199-3B (81) Designated country EP (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG) , AT, AU, BB, BG, BR, BY, CA, CH, CN, CZ, DE, DK, ES, FI, GB, HU, JP, KP, KR, KZ, LK, LU, LV, MG, MN, MW, NL, NO, NZ, PL, PT, RO, RU, SD, SE, SK, UA, US, UZ, VN (72) Inventor Bengtsson, Snes Sweden Beksche, Vickerbegen, 16 (72) Inventor Darkvist, Erik Sweden Vesterros, Gudruns, Bake, 51 [Continued summary] From the first stage in the gas supply direction for discharging the liquid containing luffid Outlet conduit (31) of
Claims (1)
Applications Claiming Priority (3)
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|---|---|---|---|
| SE9300533A SE9300533L (en) | 1993-02-18 | 1993-02-18 | Methods and apparatus for the absorption of hydrogen sulphide |
| SE9300533-8 | 1993-02-18 | ||
| PCT/SE1994/000030 WO1994019091A1 (en) | 1993-02-18 | 1994-01-18 | Process and apparatus for absorbing hydrogen sulphide |
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| JPH08506993A true JPH08506993A (en) | 1996-07-30 |
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| JP (1) | JPH08506993A (en) |
| KR (1) | KR100286384B1 (en) |
| CN (1) | CN1050527C (en) |
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| JP2010537800A (en) * | 2007-08-31 | 2010-12-09 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Method and apparatus for removing at least one hydrogenated chalcogen compound from an exhaust gas stream |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE501782C2 (en) * | 1993-09-17 | 1995-05-15 | Flaekt Ab | Method and apparatus for selectively removing hydrogen sulfide from a gas |
| JPH09183618A (en) * | 1995-12-28 | 1997-07-15 | Kansai Electric Power Co Inc:The | Production of gypsum |
| KR100347970B1 (en) * | 1999-08-11 | 2002-08-07 | 대경기계기술주식회사 | System for eliminating malodorous substance from malodorous gas |
| KR100415917B1 (en) * | 2001-11-14 | 2004-01-24 | 주식회사 포스코 | Method for cleaning expanded metal packing in hydrogen sulfide collecting tank |
| DE112005001658T5 (en) | 2004-07-12 | 2007-06-06 | Exxonmobil Upstream Research Co., Houston | Process for removing sulfur-containing compounds |
| US7727374B2 (en) * | 2004-09-23 | 2010-06-01 | Skyonic Corporation | Removing carbon dioxide from waste streams through co-generation of carbonate and/or bicarbonate minerals |
| KR100943537B1 (en) | 2008-05-27 | 2010-02-22 | 주식회사 애니텍 | An Air Cleaner with Function Capable of CO2 Removal |
| DE102009009476A1 (en) * | 2009-02-19 | 2010-08-26 | Linde-Kca-Dresden Gmbh | Process and apparatus for purifying a carbon dioxide-containing gas stream |
| US8617494B2 (en) * | 2012-03-30 | 2013-12-31 | Alstom Technology Ltd | Condenser and method for cleaning flue gases |
| CN105056709A (en) * | 2015-07-30 | 2015-11-18 | 江苏金曼科技有限责任公司 | Tail gas processing method |
| CN105854549A (en) * | 2016-05-06 | 2016-08-17 | 铜仁学院 | Mercury-containing waste gas treatment method |
| KR102325084B1 (en) * | 2019-10-04 | 2021-11-10 | 서정봉 | Composition for neutralizing acidic waste water or harmful gas having low freezing point |
| CN111330413A (en) * | 2020-02-13 | 2020-06-26 | 东营联合石化有限责任公司 | Petroleum cracking gasification substance desulfurization device |
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| SE319078B (en) * | 1968-06-07 | 1969-12-22 | British Columbia Res Council | |
| SE448173B (en) * | 1985-06-03 | 1987-01-26 | Croon Inventor Ab | PROCEDURE FOR THE RECOVERY OF CELLULOSA DISPOSAL CHEMICALS BY PYROLYSIS |
| SE9001957L (en) * | 1990-05-31 | 1991-12-01 | Chemrec Ab | Purification of process gas from partial combustion of black liquor |
| US5284550A (en) * | 1992-06-18 | 1994-02-08 | Combustion Engineering, Inc. | Black liquier gasification process operating at low pressures using a circulating fluidized bed |
-
1993
- 1993-02-18 SE SE9300533A patent/SE9300533L/en not_active Application Discontinuation
-
1994
- 1994-01-18 PL PL94310320A patent/PL180733B1/en not_active IP Right Cessation
- 1994-01-18 CA CA002156411A patent/CA2156411C/en not_active Expired - Fee Related
- 1994-01-18 KR KR1019950703518A patent/KR100286384B1/en not_active IP Right Cessation
- 1994-01-18 WO PCT/SE1994/000030 patent/WO1994019091A1/en active IP Right Grant
- 1994-01-18 JP JP6518871A patent/JPH08506993A/en active Pending
- 1994-01-18 CN CN94191218A patent/CN1050527C/en not_active Expired - Fee Related
- 1994-01-18 RU RU95118712A patent/RU2103050C1/en not_active IP Right Cessation
- 1994-01-18 AU AU61586/94A patent/AU6158694A/en not_active Abandoned
- 1994-01-18 BR BR9406271A patent/BR9406271A/en not_active IP Right Cessation
-
1995
- 1995-08-17 FI FI953882A patent/FI114084B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010537800A (en) * | 2007-08-31 | 2010-12-09 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Method and apparatus for removing at least one hydrogenated chalcogen compound from an exhaust gas stream |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2103050C1 (en) | 1998-01-27 |
| FI953882A0 (en) | 1995-08-17 |
| BR9406271A (en) | 1996-01-02 |
| CA2156411C (en) | 2004-05-11 |
| SE9300533L (en) | 1994-08-19 |
| KR100286384B1 (en) | 2001-04-16 |
| SE9300533D0 (en) | 1993-02-18 |
| FI953882A (en) | 1995-08-17 |
| WO1994019091A1 (en) | 1994-09-01 |
| CA2156411A1 (en) | 1994-09-01 |
| PL180733B1 (en) | 2001-03-30 |
| PL310320A1 (en) | 1995-12-11 |
| KR960700799A (en) | 1996-02-24 |
| CN1050527C (en) | 2000-03-22 |
| FI114084B (en) | 2004-08-13 |
| AU6158694A (en) | 1994-09-14 |
| CN1118146A (en) | 1996-03-06 |
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