JP2007038188A - Method and apparatus for desulfurizing hydrogen sulfide-containing gas - Google Patents
Method and apparatus for desulfurizing hydrogen sulfide-containing gas Download PDFInfo
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 106
- 239000007789 gas Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000003009 desulfurizing effect Effects 0.000 title abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 108
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000010521 absorption reaction Methods 0.000 claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 43
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 28
- 241000894006 Bacteria Species 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 230000007935 neutral effect Effects 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000006477 desulfuration reaction Methods 0.000 claims description 26
- 230000023556 desulfurization Effects 0.000 claims description 26
- 229910001415 sodium ion Inorganic materials 0.000 claims description 23
- 230000002745 absorbent Effects 0.000 claims description 14
- 239000002250 absorbent Substances 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000029087 digestion Effects 0.000 description 7
- 239000010802 sludge Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- -1 sulfide ions Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000010800 human waste Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000605118 Thiobacillus Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Treating Waste Gases (AREA)
- Activated Sludge Processes (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
Description
本発明は、硫化水素含有ガスの脱硫方法及び脱硫装置に関する。さらに詳しくは、本発明は、各種の工場や処理場などで発生する硫化水素と二酸化炭素を含むガスから、従来のアルカリスクラバーに比較して二酸化炭素によるｐＨ低下が少なく、硫化水素を効率よく除去することができる硫化水素含有ガスの脱硫方法及び脱硫装置に関する。 The present invention relates to a desulfurization method and a desulfurization apparatus for a hydrogen sulfide-containing gas. More specifically, the present invention removes hydrogen sulfide efficiently from gas containing hydrogen sulfide and carbon dioxide generated in various factories and treatment plants with less pH drop due to carbon dioxide compared to conventional alkaline scrubbers. The present invention relates to a desulfurization method and a desulfurization apparatus for hydrogen sulfide-containing gas.
化学工場、製紙工場、食品飲料製造工場、ゴミ焼却場、し尿処理場、下水処理場などから排出される排ガスは、硫化水素と同時に二酸化炭素を含有するものが多い。硫化水素と二酸化炭素を含有するガスの処理方法として、アルカリ吸収処理と生物酸化処理との組み合わせが検討されている。 Exhaust gas discharged from chemical factories, paper mills, food and beverage factories, garbage incineration plants, human waste treatment plants, sewage treatment plants, etc. often contains carbon dioxide as well as hydrogen sulfide. As a method for treating a gas containing hydrogen sulfide and carbon dioxide, a combination of alkali absorption treatment and biological oxidation treatment has been studied.
例えば、硫化水素含有ガスを、大容量の設備を必要とすることなく、多量のアルカリを使用することなく、低コストで効率的に処理して、硫化水素濃度の低い処理ガスを得る方法として、硫化水素を含む原ガスを活性汚泥、生物処理水又は工水と接触させて、原ガス中の硫化水素を粗取りする一次脱硫工程と、一次脱硫工程の処理ガスを湿式又は乾式でアルカリと接触させてガス中に残留する硫化水素を除去する二次脱硫工程とを有する硫化水素含有ガスの脱硫方法が提案されている（特許文献１）。 For example, as a method of obtaining a processing gas having a low hydrogen sulfide concentration by efficiently processing a hydrogen sulfide-containing gas at a low cost without using a large amount of equipment, without using a large amount of alkali, The primary gas containing hydrogen sulfide is brought into contact with activated sludge, biologically treated water or industrial water, and the hydrogen sulfide in the raw gas is roughly removed, and the treated gas in the primary desulfurizing process is contacted with alkali in a wet or dry manner. A hydrogen sulfide-containing gas desulfurization method has been proposed which includes a secondary desulfurization step of removing hydrogen sulfide remaining in the gas (Patent Document 1).
また、メタンガスの含有率を低下させず、低コストで効率よく、しかも高い脱硫率で脱硫でき、かつ脱硫に伴って新たな廃液を生じない消化ガスの脱硫方法及び装置として、有機性物質の嫌気性微生物消化により発生する消化ガスを、酸素を混合することなく、有機性物質の好気性微生物酸化における処理液からなる洗浄液のスプレー液と接触させて、消化ガス中の硫化水素を洗浄液に吸収させる吸収工程と、吸収工程で得られた吸収液を好気性微生物酸化して、吸収された硫化水素を酸化する酸化工程とを含む消化ガスの脱硫方法が提案されている（特許文献２）。 In addition, as a desulfurization method and apparatus for digestion gas that does not reduce the content of methane gas, can be efficiently desulfurized at a low cost, and can be desulfurized at a high desulfurization rate, and does not generate a new waste liquid as a result of desulfurization, The digestion gas generated by the digestive microorganism digestion is brought into contact with the spray solution of the cleaning liquid consisting of the treatment liquid in the aerobic microbial oxidation of organic substances without mixing oxygen, and the hydrogen sulfide in the digestion gas is absorbed by the cleaning liquid A digestion gas desulfurization method has been proposed that includes an absorption step and an oxidation step in which the absorption liquid obtained in the absorption step is subjected to aerobic microorganism oxidation to oxidize absorbed hydrogen sulfide (Patent Document 2).
しかし、排ガス中の二酸化炭素の濃度比が高いと、アルカリが二酸化炭素に消費され、吸収液のｐＨが低下して吸収率も低下し、硫化水素の除去率が低下するという問題があった。
本発明は、各種の工場や処理場などで発生する硫化水素と二酸化炭素を含むガスから、従来のアルカリスクラバーに比較して二酸化炭素によるｐＨ低下が少なく、硫化水素を効率よく除去することができる硫化水素含有ガスの脱硫方法及び脱硫装置を提供することを目的としてなされたものである。 The present invention is capable of efficiently removing hydrogen sulfide from a gas containing hydrogen sulfide and carbon dioxide generated in various factories and treatment plants with less pH drop due to carbon dioxide compared to a conventional alkali scrubber. The object of the present invention is to provide a desulfurization method and desulfurization apparatus for a hydrogen sulfide-containing gas.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、多量の二酸化炭素を含有する排ガス中の硫化水素を吸収するにあたり、吸収液中のアルカリ金属イオン濃度を高めることにより、効果的に硫化水素を吸収し得ることを見いだし、この知見に基づいて本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have increased the alkali metal ion concentration in the absorption liquid when absorbing hydrogen sulfide in exhaust gas containing a large amount of carbon dioxide. It has been found that hydrogen sulfide can be absorbed effectively, and the present invention has been completed based on this finding.
すなわち、本発明は、
（１）硫化水素と二酸化炭素とを含むガスを、中性塩由来のアルカリ金属イオンを除いたアルカリ金属イオン濃度が０.２５〜３.５モル／Ｌであるアルカリ性吸収液と接触させて、硫化水素を該吸収液に移行させたのち、該吸収液を硫黄酸化細菌を用いた好気性生物処理槽に供給し、該好気性生物処理槽から流出する処理液を前記アルカリ性吸収液として循環使用することを特徴とする硫化水素含有ガスの脱硫方法、
（２）アルカリ金属イオンがナトリウムイオン又はカリウムイオンであり、アルカリ金属イオンが水酸化物、炭酸塩又は重炭酸塩として供給される(１)記載の硫化水素含有ガスの脱硫方法、
（３）硫化水素と二酸化炭素とを含むガスをアルカリ性吸収液と接触させる気液接触装置、硫化水素が移行した該吸収液を硫黄酸化細菌により処理する好気性生物処理槽及び処理された吸収液を気液接触装置に送液する送液路を有することを特徴とする硫化水素含有ガスの脱硫装置、及び、
（４）硫化水素と二酸化炭素とを含むガスをアルカリ性吸収液と接触させる気液接触装置、硫化水素が移行した該吸収液を硫黄酸化細菌により処理する好気性生物処理槽、処理された吸収液を固液分離する固液分離部及び固液分離された液を気液接触装置に送液する送液路を有することを特徴とする硫化水素含有ガスの脱硫装置、
を提供するものである。
That is, the present invention
(1) contacting a gas containing hydrogen sulfide and carbon dioxide with an alkaline absorbent having an alkali metal ion concentration of 0.25 to 3.5 mol / L excluding alkali metal ions derived from neutral salts; After transferring hydrogen sulfide to the absorption liquid, the absorption liquid is supplied to an aerobic biological treatment tank using sulfur-oxidizing bacteria, and the treatment liquid flowing out of the aerobic biological treatment tank is recycled as the alkaline absorption liquid. A method for desulfurizing a hydrogen sulfide-containing gas, characterized by:
(2) The method for desulfurizing a hydrogen sulfide-containing gas according to (1), wherein the alkali metal ion is sodium ion or potassium ion, and the alkali metal ion is supplied as a hydroxide, carbonate or bicarbonate,
(3) Gas-liquid contact device for bringing a gas containing hydrogen sulfide and carbon dioxide into contact with an alkaline absorbent, an aerobic biological treatment tank for treating the absorbent with transferred hydrogen sulfide with sulfur-oxidizing bacteria, and a treated absorbent A desulfurization device for hydrogen sulfide-containing gas, characterized by having a liquid feed passage for feeding the gas to a gas-liquid contact device, and
(4) Gas-liquid contact device for bringing a gas containing hydrogen sulfide and carbon dioxide into contact with an alkaline absorbent, an aerobic biological treatment tank for treating the absorbent with transferred hydrogen sulfide with sulfur-oxidizing bacteria, and a treated absorbent A desulfurization apparatus for a hydrogen sulfide-containing gas, comprising: a solid-liquid separation unit for solid-liquid separation; and a liquid feeding path for feeding the solid-liquid separated liquid to a gas-liquid contact device,
Is to provide.
本発明の硫化水素含有ガスの脱硫方法及び脱硫装置によれば、高濃度の二酸化炭素を含む硫化水素含有ガスをアルカリ性吸収液を用いて処理して、二酸化炭素によるアルカリの消費にもとづく吸収液のｐＨの低下が少なく、効果的に硫化水素を高い除去率で除去することができる。 According to the hydrogen sulfide-containing gas desulfurization method and desulfurization apparatus of the present invention, a hydrogen sulfide-containing gas containing high-concentration carbon dioxide is treated with an alkaline absorption liquid, and the absorption liquid based on the consumption of alkali by carbon dioxide is obtained. There is little decrease in pH, and hydrogen sulfide can be effectively removed at a high removal rate.
本発明の硫化水素含有ガスの脱硫方法においては、硫化水素と二酸化炭素とを含むガスを、中性塩由来のアルカリ金属イオンを除いたアルカリ金属イオン濃度が０.２５〜３.５モル／Ｌであるアルカリ性吸収液と接触させて、硫化水素を該吸収液に移行させたのち、該吸収液を硫黄酸化細菌を用いた好気性生物処理槽に供給し、該好気性生物処理槽から流出する処理液を前記アルカリ性吸収液として循環使用する。 In the hydrogen sulfide-containing gas desulfurization method of the present invention, the alkali metal ion concentration of the gas containing hydrogen sulfide and carbon dioxide, excluding alkali metal ions derived from neutral salts, is 0.25 to 3.5 mol / L. The hydrogen sulfide is transferred to the absorption liquid by being brought into contact with the alkaline absorption liquid, and then the absorption liquid is supplied to the aerobic biological treatment tank using sulfur-oxidizing bacteria and flows out of the aerobic biological treatment tank. The treatment liquid is circulated and used as the alkaline absorbing liquid.
図１は、本発明方法の一態様の工程系統図である。本態様においては、硫化水素と二酸化炭素とを含むガスを充填塔１に送り、塔頂の液分散器２から供給される中性塩由来のアルカリ金属イオンを除いたアルカリ金属イオン濃度が０.２５〜３.５モル／Ｌのアルカリ性吸収液と接触させる。ガス中の硫化水素は、アルカリ性吸収液に移行し、硫化水素の大部分が除去されたガスが塔頂の排気管から排出される。硫化水素を吸収したアルカリ性吸収液は、送液管３を経由して好気性生物処理槽４へ送られる。好気性生物処理槽は、好気性酸化部５と必要により固液分離部６からなり、好気性酸化部において槽底の散気管７から空気が供給され、硫化物イオンが硫黄酸化細菌により酸化されて硫黄単体、亜硫酸イオン、硫酸イオンなどになる。前記生物処理槽からの処理液の一部は、ポンプ８により返送液管９を経由して充填塔に送られ、アルカリ性吸収液として循環使用される。好気性生物処理槽あるいは充填塔に送られる処理液には、アルカリ水溶液が添加されて、アルカリ金属イオン濃度が調整される。処理液の残部は、排水として処理される。
FIG. 1 is a process flow diagram of one embodiment of the method of the present invention. In this embodiment, the gas containing hydrogen sulfide and carbon dioxide is sent to the packed column 1 and the alkali metal ion concentration excluding the alkali metal ions derived from the neutral salt supplied from the liquid disperser 2 at the top of the column is 0. Contact with 25-3.5 mol / L alkaline absorbent. The hydrogen sulfide in the gas moves to the alkaline absorbing liquid, and the gas from which most of the hydrogen sulfide has been removed is discharged from the exhaust pipe at the top of the tower. The alkaline absorbing liquid that has absorbed hydrogen sulfide is sent to the aerobic biological treatment tank 4 via the liquid feeding pipe 3. The aerobic biological treatment tank includes an
本発明方法は、下水、し尿、産業排水、汚泥などの有機性物質の嫌気性微生物消化により発生する消化ガスなどの少量の硫化水素と多量の二酸化炭素を含有するガスの脱硫に好適に適用することができる。硫化水素は、水中で解離して水硫化イオン（ＨＳ-）となり、吸収除去される。吸収液に移行した硫化水素は、液のアルカリ性が強いと解離割合が多くなるために、アルカリ性の方が効率よく吸収除去される。しかし、被処理ガス中に二酸化炭素が多く存在すると、アルカリ性の吸収液は二酸化炭素を多く吸収して、そのｐＨを低下させてしまい、硫化水素の解離が妨げられ、結果として硫化水素の吸収除去が効率的に進行しなくなる。本発明方法によれば、硫化水素含有ガス中に二酸化炭素が多量に存在しても、アルカリ性吸収液のｐＨを比較的高めに保持することができ、硫化水素を効率よく除去することができる。 The method of the present invention is suitably applied to desulfurization of a gas containing a small amount of hydrogen sulfide and a large amount of carbon dioxide such as digestion gas generated by anaerobic microbial digestion of organic substances such as sewage, human waste, industrial wastewater, and sludge. be able to. Hydrogen sulfide is dissociated in water to form hydrosulfide ions (HS − ) and is absorbed and removed. The hydrogen sulfide transferred to the absorbing solution has a higher dissociation ratio when the alkalinity of the solution is strong, so that the alkali is more efficiently absorbed and removed. However, if a large amount of carbon dioxide is present in the gas to be treated, the alkaline absorbing solution absorbs a large amount of carbon dioxide and lowers its pH, preventing the dissociation of hydrogen sulfide, resulting in the absorption and removal of hydrogen sulfide. Will not proceed efficiently. According to the method of the present invention, even when a large amount of carbon dioxide is present in the hydrogen sulfide-containing gas, the pH of the alkaline absorbent can be kept relatively high, and hydrogen sulfide can be efficiently removed.
本発明方法に用いるアルカリ性吸収液は、中性塩由来のアルカリ金属イオンを除いたアルカリ金属イオン濃度の濃度が０.２５〜３.５モル／Ｌであり、より好ましくは０.５〜２.５モル／Ｌである。中性塩由来のアルカリ金属イオンを除いたアルカリ金属イオン濃度が０.２５モル／Ｌ未満であると、二酸化炭素の吸収によるｐＨ低下のために硫化水素の吸収効率が低く、硫化水素の除去率が低下して、処理ガスの硫化水素濃度が十分に下がらないおそれがある。中性塩由来のアルカリ金属イオンを除いたアルカリ金属イオン濃度が３.５モル／Ｌを超えると、重炭酸ナトリウム塩などの析出が起こり、偏流によりガス吸収反応が進みにくくなって、硫化水素の除去率が低下し、処理ガスの硫化水素濃度が十分に下がらないか、あるいは、処理液が流れないおそれがある。 The alkaline absorbing liquid used in the method of the present invention has an alkali metal ion concentration of 0.25 to 3.5 mol / L excluding alkali metal ions derived from neutral salts, and more preferably 0.5 to 2.5. 5 mol / L. When the alkali metal ion concentration excluding alkali metal ions derived from neutral salts is less than 0.25 mol / L, the absorption efficiency of hydrogen sulfide is low due to the decrease in pH due to absorption of carbon dioxide, and the removal rate of hydrogen sulfide. May decrease, and the hydrogen sulfide concentration of the processing gas may not be sufficiently reduced. When the alkali metal ion concentration excluding alkali metal ions derived from neutral salts exceeds 3.5 mol / L, precipitation of sodium bicarbonate salt and the like occurs, and the gas absorption reaction is difficult to proceed due to drift, and hydrogen sulfide There is a possibility that the removal rate is lowered and the hydrogen sulfide concentration of the processing gas is not sufficiently lowered or the processing liquid does not flow.
中性塩は、水に溶かすとほぼ中性を示す塩であり、強酸と強塩基の中和により生成する正塩である。本発明方法においては、中性塩のカチオン成分がアルカリ金属イオンなので、中性塩のアニオン成分は、硫酸イオン、塩化物イオン、硝酸イオンなどである。中性塩由来のアルカリ金属イオンを除いたアルカリ金属イオン濃度は、アルカリ性吸収液中の全アルカリ金属イオン濃度と、中性塩の各アニオン成分の濃度を測定し、全アルカリ金属イオン濃度から、各アニオン成分の濃度の当量に相当する量を減ずることによって求めることができる。簡易的には、Ｍアルカリ度（ｐＨ４.８酸消費量）を測定することで求めることができる。 A neutral salt is a salt that is almost neutral when dissolved in water, and is a normal salt formed by neutralization of a strong acid and a strong base. In the method of the present invention, since the cation component of the neutral salt is an alkali metal ion, the anion component of the neutral salt is sulfate ion, chloride ion, nitrate ion or the like. The alkali metal ion concentration excluding the alkali metal ions derived from the neutral salt was determined by measuring the total alkali metal ion concentration in the alkaline absorbent and the concentration of each anion component of the neutral salt. It can be determined by reducing the amount corresponding to the equivalent of the concentration of the anion component. In simple terms, it can be determined by measuring the M alkalinity (pH 4.8 acid consumption).
本発明方法に用いる硫黄酸化細菌としては、例えば、チオバチルス属、チオトリックス属、ベギアトア属、チオマリヌス属、シュードモナス属などの細菌を挙げることができる。本発明方法においては、硫化水素含有ガスの処理に先立って、硫黄酸化細菌を下水、産業排水などの活性汚泥から馴養することが好ましい。硫黄酸化細菌の馴養は、硫化ナトリウム、チオ硫酸塩、亜硫酸塩などの不揮発性の還元性硫黄化合物を用いて行うことが好ましい。不揮発性の還元性硫黄化合物を用いることにより、還元性硫黄化合物の放散による大気汚染を防止することができる。好気性活性汚泥法により発生した活性汚泥を好気性生物処理槽に入れ、不揮発性の還元性化合物とアンモニア、リンなどの栄養源を溶解した溶液を供給し、曝気しつつ処理することにより、硫黄酸化細菌を馴養することができる。好気性生物処理槽液の還元性硫黄化合物が検出されなくなることにより、硫黄酸化細菌の馴養の完了を確認することができる。 Examples of the sulfur-oxidizing bacterium used in the method of the present invention include bacteria such as thiobacillus genus, thiotrix genus, begiatoa genus, thiomarinus genus, and pseudomonas genus. In the method of the present invention, it is preferable to acclimate sulfur-oxidizing bacteria from activated sludge such as sewage and industrial wastewater prior to the treatment of the hydrogen sulfide-containing gas. Acclimatization of sulfur-oxidizing bacteria is preferably performed using a non-volatile reducing sulfur compound such as sodium sulfide, thiosulfate, or sulfite. By using a non-volatile reducing sulfur compound, air pollution due to the emission of the reducing sulfur compound can be prevented. Activated sludge generated by the aerobic activated sludge method is placed in an aerobic biological treatment tank, and a solution in which nutrient sources such as non-volatile reducing compounds and ammonia and phosphorus are dissolved is supplied. You can acclimatize oxidized bacteria. The completion of acclimatization of the sulfur-oxidizing bacteria can be confirmed by the detection of the reducing sulfur compound in the aerobic biological treatment tank liquid.
本発明方法においては、アルカリ金属イオンがナトリウムイオン又はカリウムイオンであることが好ましい。ナトリウムイオン又はカリウムイオンを含有するアルカリ性吸収液は、硫化水素の移行性が良好であり、効率的に硫化水素を吸収して除去することができる。本発明方法においては、アルカリ金属イオンが、水酸化物、炭酸塩、重炭酸塩として供給されることが好ましい。ヒドロキシルイオン、炭酸イオン又は重炭酸イオンを含有するアルカリ性吸収液は、硫化水素の移行性が良好であり、効率的に硫化水素を吸収して除去することができる。 In the method of the present invention, the alkali metal ion is preferably a sodium ion or a potassium ion. Alkaline absorption liquids containing sodium ions or potassium ions have good hydrogen sulfide migration, and can efficiently absorb and remove hydrogen sulfide. In the method of the present invention, alkali metal ions are preferably supplied as hydroxides, carbonates, and bicarbonates. Alkaline absorption liquids containing hydroxyl ions, carbonate ions or bicarbonate ions have good hydrogen sulfide migration, and can efficiently absorb and remove hydrogen sulfide.
本発明の硫化水素含有ガスの脱硫装置の第一の態様は、硫化水素と二酸化炭素とを含むガスをアルカリ性吸収液と接触させる気液接触装置、硫化水素が移行した該吸収液を硫黄酸化細菌により処理する好気性生物処理槽及び処理された吸収液を気液接触装置に送液する送液路を有する装置である。
本発明の硫化水素含有ガスの脱硫装置の第二の態様は、硫化水素と二酸化炭素とを含むガスをアルカリ性吸収液と接触させる気液接触装置、硫化水素が移行した該吸収液を硫黄酸化細菌により処理する好気性生物処理槽、処理された吸収液を固液分離する固液分離部及び固液分離された液を気液接触装置に送液する送液路を有する装置である。
A first aspect of the desulfurization apparatus for hydrogen sulfide-containing gas of the present invention is a gas-liquid contact apparatus for bringing a gas containing hydrogen sulfide and carbon dioxide into contact with an alkaline absorption liquid, and the absorption liquid to which hydrogen sulfide has been transferred is converted into a sulfur-oxidizing bacterium. The apparatus has an aerobic biological treatment tank to be treated and a liquid feed path for feeding the treated absorption liquid to the gas-liquid contact device.
The second aspect of the desulfurization apparatus for hydrogen sulfide-containing gas of the present invention is a gas-liquid contact apparatus for bringing a gas containing hydrogen sulfide and carbon dioxide into contact with an alkaline absorption liquid, and the absorption liquid to which hydrogen sulfide has migrated is converted into a sulfur-oxidizing bacterium. An aerobic biological treatment tank to be treated by the above, a solid-liquid separation part for solid-liquid separation of the treated absorption liquid, and a liquid feed path for feeding the solid-liquid separated liquid to the gas-liquid contact device.
本発明装置に用いる気液接触装置に特に制限はなく、例えば、充填塔、濡れ壁塔、段塔、スプレー塔、スクラバー、気泡塔、気泡撹拌槽などを挙げることができる。これらの中で、充填塔及びスプレー塔を好適に用いることができる。充填塔は、構造が簡単で取り扱いが容易であり、ガスの圧力損失が少ない。スプレー塔は、液の噴霧にかなりの動力が必要であるが、構造が簡単で建設費が安く、ガスの圧力損失が少ない。スプレー塔には、液の飛沫同伴を防止する手段を設けることが好ましい。 There are no particular limitations on the gas-liquid contact device used in the apparatus of the present invention, and examples thereof include a packed tower, a wet wall tower, a plate tower, a spray tower, a scrubber, a bubble tower, and a bubble stirring tank. Among these, a packed tower and a spray tower can be preferably used. The packed tower has a simple structure, is easy to handle, and has a low pressure loss of gas. The spray tower requires considerable power to spray the liquid, but has a simple structure, low construction cost, and low gas pressure loss. The spray tower is preferably provided with means for preventing liquid entrainment.
本発明装置に用いる好気性生物処理槽に特に制限はなく、例えば、機械撹拌式エアレーションタンク、散気式エアレーションタンクのいずれをも用いることができる。好気性生物処理方式に特に制限はなく、例えば、押出流れ型又は完全混合型の標準活性汚泥法、ステップエアレーション法、コンタクトスタビリゼーション法などを挙げることができる。なお、必要に応じて、処理された処理液を固液分離するための固液分離部を設けてもよい。 There is no restriction | limiting in particular in the aerobic biological treatment tank used for this invention apparatus, For example, any of a mechanical stirring type aeration tank and an aeration type aeration tank can be used. The aerobic biological treatment method is not particularly limited, and examples thereof include an extruded flow type or a fully mixed type standard activated sludge method, a step aeration method, and a contact stabilization method. In addition, you may provide the solid-liquid separation part for carrying out solid-liquid separation of the processed process liquid as needed.
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
なお、実施例及び比較例において、液中に存在するＨ2Ｓ、ＨＳ-及びＳ2-の硫黄の合計を、全Ｓ2-と表示する。全Ｓ2-濃度は、溶存硫化物測定用検知管［光明理化学工業(株)、２００ＳＢ］を用いて測定した。また、実施例及び比較例において表示されるナトリウムイオン濃度は、液中に存在する中性塩に由来するナトリウムイオンを除いたナトリウムイオン濃度である。ナトリウムイオン濃度は、ＪＩＳ Ｋ ０１０２ １５.１にしたがって酸消費量（ｐＨ４.８）を測定することにより求めた。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the examples and comparative examples, the total of sulfur in H 2 S, HS − and S 2− present in the liquid is expressed as all S 2− . The total S 2− concentration was measured using a detector tube for measuring dissolved sulfide [Komei Chemical Co., Ltd., 200SB]. Moreover, the sodium ion concentration displayed in an Example and a comparative example is a sodium ion concentration except the sodium ion derived from the neutral salt which exists in a liquid. The sodium ion concentration was determined by measuring the acid consumption (pH 4.8) according to JIS K 0102 15.1.
実施例１
化学工場の高負荷嫌気処理設備から発生する嫌気性バイオガスと類似の試験用混合ガスを用いて、図１に示す硫黄酸化槽を備えた充填塔ガス吸収方式の生物脱硫試験を行った。
試験用混合ガスの組成は、二酸化炭素２９.８５体積％、硫化水素０.１５体積％、窒素７０.００体積％である。充填塔の寸法は、内径３０ｍｍ、高さ４,０００ｍｍであり、称呼寸法６ｍｍの磁製ラシヒリングを高さ２,５００ｍｍまで充填した。硫黄酸化槽の寸法は、長さ３００ｍｍ、幅１００ｍｍ、高さ６００ｍｍ、実容量１０Ｌであり、工場排水の活性汚泥混合液を槽に入れ、チオ硫酸ナトリウム５５０ｍｇ／Ｌを添加した工場排水を２週間供給して硫黄酸化細菌の馴養を行ったのち、試験を開始した。
充填塔に試験用混合ガスを３５０Ｌ(標準状態)／ｈ流入させ、硫黄酸化槽から流出する処理液をアルカリ性吸収液として３４Ｌ／ｈ循環させた。硫黄酸化槽に０.６モル／Ｌ水酸化ナトリウム水溶液を添加して、ｐＨ８.８及び循環吸収液のＭアルカリ度が０.５モル／Ｌを保たれるように制御した。硫黄酸化細菌により吸収された硫化水素の一部は硫酸イオンにまで酸化されるために、Ｍアルカリ度は０.６モル／Ｌより低下し、約０.５モル／Ｌとなった。充填塔入口のｐＨは硫黄酸化槽と同じｐＨ８.８であったが、吸収塔内で二酸化炭素、硫化水素などの酸性ガスを吸収するために、充填塔出口のｐＨは８.３まで低下した。このとき、充填塔から排出される処理ガスの硫化水素濃度は３０ｐｐｍ（体積比）であり、硫化水素の除去率は９８.０％であった。
実施例２
硫黄酸化槽のｐＨ制御用の水酸化ナトリウム水溶液の濃度を２.７モル／Ｌとした以外は、実施例１と同じ操作を行い、硫黄酸化槽のｐＨを８.８に制御した。硫黄酸化細菌により吸収された硫化水素の一部は硫酸イオンにまで酸化されるために、Ｍアルカリ度は２.７モル／Ｌより低下し、約２.５モル／Ｌとなった。充填塔出口のｐＨは８.７で、充填塔から排出される処理ガスの硫化水素濃度は２５ｐｐｍ（体積比）であり、硫化水素の除去率は９８.３％であった。
Example 1
Using a mixed gas for test similar to anaerobic biogas generated from a high-load anaerobic treatment facility in a chemical factory, a biodesulfurization test of a packed tower gas absorption system equipped with a sulfur oxidation tank shown in FIG. 1 was conducted.
The composition of the test gas mixture is 29.85% by volume of carbon dioxide, 0.15% by volume of hydrogen sulfide, and 70.00% by volume of nitrogen. The dimensions of the packed tower were an inner diameter of 30 mm and a height of 4,000 mm, and a magnetic Raschig ring having a nominal dimension of 6 mm was packed to a height of 2500 mm. The dimensions of the sulfur oxidation tank are length 300mm, width 100mm, height 600mm, actual capacity 10L, put the activated sludge mixed liquid of factory wastewater into the tank, and add factory wastewater with sodium thiosulfate 550mg / L for 2 weeks After supplying and acclimatizing the sulfur-oxidizing bacteria, the test was started.
The test mixed gas was introduced into the packed tower at 350 L (standard state) / h, and the treatment liquid flowing out from the sulfur oxidation tank was circulated as 34 L / h as an alkaline absorbent. A 0.6 mol / L sodium hydroxide aqueous solution was added to the sulfur oxidation tank to control the pH 8.8 and the M alkalinity of the circulating absorbent to be maintained at 0.5 mol / L. Part of the hydrogen sulfide absorbed by the sulfur-oxidizing bacteria is oxidized to sulfate ions, so that the M alkalinity is reduced from 0.6 mol / L to about 0.5 mol / L. The pH at the inlet of the packed tower was 8.8, the same as that of the sulfur oxidation tank, but the pH at the outlet of the packed tower was lowered to 8.3 in order to absorb acidic gases such as carbon dioxide and hydrogen sulfide in the absorption tower. . At this time, the hydrogen sulfide concentration of the processing gas discharged from the packed tower was 30 ppm (volume ratio), and the removal rate of hydrogen sulfide was 98.0%.
Example 2
The same operation as in Example 1 was performed except that the concentration of the sodium hydroxide aqueous solution for pH control of the sulfur oxidation tank was 2.7 mol / L, and the pH of the sulfur oxidation tank was controlled to 8.8. Part of the hydrogen sulfide absorbed by the sulfur-oxidizing bacteria was oxidized to sulfate ions, so that the M alkalinity decreased from 2.7 mol / L to about 2.5 mol / L. The pH at the outlet of the packed tower was 8.7, the hydrogen sulfide concentration of the processing gas discharged from the packed tower was 25 ppm (volume ratio), and the removal rate of hydrogen sulfide was 98.3%.
比較例１
硫黄酸化槽のｐＨ制御用の水酸化ナトリウム水溶液の濃度を０.１１モル／Ｌとした以外は、実施例１と同じ操作を行い、硫黄酸化槽のｐＨを８.８に制御した。このとき、充填塔出口から流出する吸収液のｐＨは７.３で、充填塔から排出される処理ガスの硫化水素濃度は１３０ｐｐｍ（体積比）であり、硫化水素の除去率は９１.３％であった。
比較例２
硫黄酸化槽のｐＨ制御用の水酸化ナトリウム水溶液の濃度を５.０モル／Ｌとした以外は、実施例１と同じ操作を行い、硫黄酸化槽のｐＨを８.８に制御した。硫黄酸化槽の周囲の壁や吸収塔内部に重炭酸ナトリウムと思われる析出物が観察された。この析出物のために吸収塔内で偏流が起こったためか、充填塔から排出される処理ガスの硫化水素濃度は安定せず、平均で９０ｐｐｍ（体積比）であった。さらに運転を継続すると、充填塔の差圧が上昇してガスを流せなくなった。
実施例１〜２及び比較例１〜２の結果を、第１表に示す。
Comparative Example 1
The same operation as in Example 1 was performed except that the concentration of the sodium hydroxide aqueous solution for controlling the pH of the sulfur oxidation tank was 0.11 mol / L, and the pH of the sulfur oxidation tank was controlled to 8.8. At this time, the pH of the absorption liquid flowing out from the packed tower outlet is 7.3, the hydrogen sulfide concentration of the processing gas discharged from the packed tower is 130 ppm (volume ratio), and the removal rate of hydrogen sulfide is 91.3%. Met.
Comparative Example 2
The same operation as in Example 1 was performed except that the concentration of the sodium hydroxide aqueous solution for pH control of the sulfur oxidation tank was 5.0 mol / L, and the pH of the sulfur oxidation tank was controlled to 8.8. Precipitates that seem to be sodium bicarbonate were observed on the wall around the sulfur oxidation tank and inside the absorption tower. The concentration of hydrogen sulfide in the treatment gas discharged from the packed tower was not stable and averaged 90 ppm (volume ratio) because of the precipitating flow in the absorption tower due to this deposit. When the operation was continued further, the differential pressure in the packed tower increased and gas could not flow.
The results of Examples 1-2 and Comparative Examples 1-2 are shown in Table 1.
第１表に見られるように、中性塩由来のナトリウムイオンを除いたナトリウムイオン濃度が０.５モル／Ｌ又は２.５モル／Ｌである実施例１〜２においては、充填塔における硫化水素の除去率が高く、処理ガス中の硫化水素濃度が３０ｐｐｍ（体積比）以下となっている。これに対して、中性塩由来のナトリウムイオンを除いたナトリウムイオン濃度が０.１モル／Ｌである比較例１においては、充填塔における硫化水素の除去率が低く、処理ガス中の硫化水素濃度が１３０ｐｐｍ（体積比）となっている。中性塩由来のナトリウムイオンを除いたナトリウムイオン濃度が５.０モル／Ｌである比較例２における硫化水素除去率の低下は、析出物により充填塔で偏流を起こしたためと考えられる。なお、炭酸塩が蓄積して、安定運転は続けられなかった。 As seen in Table 1, in Examples 1 and 2 where the sodium ion concentration excluding sodium ions derived from neutral salts is 0.5 mol / L or 2.5 mol / L, sulfurization in a packed column The removal rate of hydrogen is high, and the concentration of hydrogen sulfide in the processing gas is 30 ppm (volume ratio) or less. On the other hand, in Comparative Example 1 where the sodium ion concentration excluding sodium ions derived from neutral salts is 0.1 mol / L, the removal rate of hydrogen sulfide in the packed tower is low, and hydrogen sulfide in the process gas The concentration is 130 ppm (volume ratio). The decrease in the hydrogen sulfide removal rate in Comparative Example 2 in which the sodium ion concentration excluding sodium ions derived from neutral salts is 5.0 mol / L is considered to be caused by drift in the packed tower due to the precipitate. In addition, carbonate accumulated and stable operation could not be continued.
参考例１
脱イオン水に水酸化ナトリウムを溶解して、ナトリウムイオン濃度０.１モル／Ｌ、０.２５モル／Ｌ、０.５モル／Ｌ、１.０モル／Ｌ、２.５モル／Ｌ、５.０モル／Ｌの水溶液を調製した。これらの水溶液をろ過板付洗浄びんに入れ、試験用混合ガスを通気し、試験用混合ガスが平衡に達した溶液を得た。得られた平衡溶液について、ｐＨ及び全Ｓ2-濃度を測定した。結果を、第２表に示す。
Reference example 1
Sodium hydroxide is dissolved in deionized water to obtain a sodium ion concentration of 0.1 mol / L, 0.25 mol / L, 0.5 mol / L, 1.0 mol / L, 2.5 mol / L, A 5.0 mol / L aqueous solution was prepared. These aqueous solutions were put into a washing bottle with a filter plate, and a test mixed gas was vented to obtain a solution in which the test mixed gas reached equilibrium. The resulting equilibrium solution was measured for pH and total S 2− concentration. The results are shown in Table 2.
第２表に見られるように、ナトリウムイオン濃度が高いほど、試験用混合ガスと平衡に達した溶液のｐＨが高く、かつ全Ｓ2-濃度が高くなる。ナトリウムイオン濃度１モル／Ｌの水溶液は、ナトリウムイオン濃度０.１モル／Ｌのものと比べると、約１０倍の全Ｓ2-を溶解することができる。 As can be seen in Table 2, the higher the sodium ion concentration, the higher the pH of the solution that has reached equilibrium with the test gas mixture and the higher the total S 2− concentration. An aqueous solution having a sodium ion concentration of 1 mol / L can dissolve about 10 times as much total S 2− as that of a sodium ion concentration of 0.1 mol / L.
参考例２
試験用混合ガスとして、ガスＡ（二酸化炭素１.００体積％、硫化水素０.１５体積％、窒素９８.８５体積％）、ガスＢ（二酸化炭素５.００体積％、硫化水素０.１５体積％、窒素９４.８５体積％）、ガスＣ（二酸化炭素１０.００体積％、硫化水素０.１５体積％、窒素８９.８５体積％）、ガスＤ（二酸化炭素３０.００体積％、硫化水素０.１５体積％、窒素６９.８５体積％）又はガスＥ（二酸化炭素５０.００体積％、硫化水素０.１５体積％、窒素４９.８５体積％）を用い、充填塔入口の吸収液のナトリウムイオン濃度を０.１モル／Ｌ、０.５モル／Ｌ、１.０モル／Ｌ、２.５モル／Ｌ、３.５モル／Ｌ又は５.０モル／Ｌに調整して、実施例１と同じ操作を行い、定常状態に達したときの充填塔から流出する吸収液のｐＨを測定した。
試験用混合ガスの二酸化炭素濃度及びナトリウムイオン濃度と吸収液のｐＨの関係を、第３表に示す。
Reference example 2
As test gas mixtures, gas A (1.00% by volume of carbon dioxide, 0.15% by volume of hydrogen sulfide, 98.85% by volume of nitrogen), gas B (5.00% by volume of carbon dioxide, 0.15% by volume of hydrogen sulfide) %, Nitrogen 94.85% by volume), gas C (10.0% by volume of carbon dioxide, 0.15% by volume of hydrogen sulfide, 89.85% by volume of nitrogen), gas D (30.00% by volume of carbon dioxide, hydrogen sulfide) 0.15 vol%, nitrogen 69.85 vol%) or gas E (carbon dioxide 50.00 vol%, hydrogen sulfide 0.15 vol%, nitrogen 49.85 vol%) The sodium ion concentration was adjusted to 0.1 mol / L, 0.5 mol / L, 1.0 mol / L, 2.5 mol / L, 3.5 mol / L or 5.0 mol / L, The same operation as in Example 1 was performed, and the pH of the absorbing solution flowing out from the packed tower when the steady state was reached was measured.
Table 3 shows the relationship between the carbon dioxide concentration and sodium ion concentration of the test gas mixture and the pH of the absorbing solution.
第３表に見られるように、二酸化炭素濃度が高い場合は、ナトリウムイオン濃度が３.５モル／Ｌを超えると、析出物が発生するために、ナトリウムイオン濃度には上限がある。一般的に、工場において二酸化炭素濃度が大幅に変動することはないので、平均的な二酸化炭素濃度に合わせて、ナトリウムイオン濃度を決定することができる。 As seen in Table 3, when the carbon dioxide concentration is high, precipitates are generated when the sodium ion concentration exceeds 3.5 mol / L, so that there is an upper limit on the sodium ion concentration. Generally, since the carbon dioxide concentration does not fluctuate greatly in a factory, the sodium ion concentration can be determined in accordance with the average carbon dioxide concentration.
本発明の硫化水素含有ガスの脱硫方法及び脱硫装置によれば、高濃度の二酸化炭素を含む硫化水素含有ガスをアルカリ性吸収液を用いて処理して、二酸化炭素によるアルカリの消費にもとづく吸収液のｐＨの低下が少なく、効果的に硫化水素を高い除去率で除去することができる。 According to the hydrogen sulfide-containing gas desulfurization method and desulfurization apparatus of the present invention, a hydrogen sulfide-containing gas containing high-concentration carbon dioxide is treated with an alkaline absorption liquid, and the absorption liquid based on the consumption of alkali by carbon dioxide is obtained. There is little decrease in pH, and hydrogen sulfide can be effectively removed at a high removal rate.
１ 充填塔
２ 液分散器
３ 送液管
４ 好気性生物処理槽
５ 好気性酸化部
６ 固液分離部
７ 散気管
８ ポンプ
９ 返送液管
DESCRIPTION OF SYMBOLS 1 Packing tower 2 Liquid disperser 3 Liquid supply pipe 4 Aerobic
Claims (4)
A gas-liquid contact device for contacting a gas containing hydrogen sulfide and carbon dioxide with an alkaline absorbent, an aerobic biological treatment tank for treating the absorbed liquid to which hydrogen sulfide has been transferred with sulfur-oxidizing bacteria, and a solid solution for the treated absorbent A desulfurization apparatus for a hydrogen sulfide-containing gas, comprising: a solid-liquid separation unit for separation; and a liquid feed path for feeding the liquid separated into a gas-liquid contact device.
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| CN104211270A (en) * | 2014-10-11 | 2014-12-17 | 江苏同禾药业有限公司 | Method for treating cyclization waste water in production process of lipoic acid |
| KR20160071185A (en) * | 2014-12-11 | 2016-06-21 | 강석웅 | Biogas desulfurization apparatus |
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