JPS585087B2 - Gas congobutsukara CO2 obunrisuruhouhou oyobi - Google Patents
Gas congobutsukara CO2 obunrisuruhouhou oyobiInfo
- Publication number
- JPS585087B2 JPS585087B2 JP48100380A JP10038073A JPS585087B2 JP S585087 B2 JPS585087 B2 JP S585087B2 JP 48100380 A JP48100380 A JP 48100380A JP 10038073 A JP10038073 A JP 10038073A JP S585087 B2 JPS585087 B2 JP S585087B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- absorption
- weight
- potassium
- borate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 52
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 26
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910020246 KBO2 Inorganic materials 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 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 claims description 10
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- AMAGVGJJHVRPSI-UHFFFAOYSA-N potassium vanadium Chemical compound [K].[V] AMAGVGJJHVRPSI-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 87
- 238000010521 absorption reaction Methods 0.000 description 54
- 238000007790 scraping Methods 0.000 description 28
- 235000011181 potassium carbonates Nutrition 0.000 description 24
- 150000003681 vanadium Chemical class 0.000 description 24
- 239000007789 gas Substances 0.000 description 19
- 238000007792 addition Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 239000006259 organic additive Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- 229910021144 KVO3 Inorganic materials 0.000 description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 description 5
- 150000002169 ethanolamines Chemical class 0.000 description 5
- 238000010525 oxidative degradation reaction Methods 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- -1 amine borates Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- RWQVIBSTNMDLOW-UHFFFAOYSA-N O.O.O.O.O.O.O.O.[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound O.O.O.O.O.O.O.O.[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] RWQVIBSTNMDLOW-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- STNGULMWFPMOCE-UHFFFAOYSA-N ethyl 4-butyl-3,5-dimethyl-1h-pyrrole-2-carboxylate Chemical compound CCCCC1=C(C)NC(C(=O)OCC)=C1C STNGULMWFPMOCE-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- WKCZSFRAGKIIKN-UHFFFAOYSA-N 2-(4-tert-butylphenyl)ethanamine Chemical compound CC(C)(C)C1=CC=C(CCN)C=C1 WKCZSFRAGKIIKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 229910019501 NaVO3 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 101150113811 abo2 gene Proteins 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ARYAXLASPXUYJM-UHFFFAOYSA-N disodium oxido(oxo)borane Chemical compound [Na+].[Na+].[O-]B=O.[O-]B=O ARYAXLASPXUYJM-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical class [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- JAKYJVJWXKRTSJ-UHFFFAOYSA-N sodium;oxido(oxo)borane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B=O JAKYJVJWXKRTSJ-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical class [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000012224 working solution 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
- B01D53/14—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 by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
- Carbon And Carbon Compounds (AREA)
Description
【発明の詳細な説明】
本発明は炭酸カリウムの水性溶液によるガス混合物から
のＣＯ２除去に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the removal of CO2 from gas mixtures by an aqueous solution of potassium carbonate.
言うまでもなく水性炭酸カリウム溶液はガス混合物から
のＣＯ２除去に対して良く知られている。Of course, aqueous potassium carbonate solutions are well known for removing CO2 from gas mixtures.
水性炭酸カリウム溶液を用いる最も効率的な方法、例え
ば米国特許第２８８６４０５号明細書に記載されたタイ
プの方法等はいわゆる熱吸収法を用い、その場合大部分
の吸収は、該溶液の大気圧での沸点に近い高められた温
度で行なわれる。The most efficient methods using aqueous potassium carbonate solutions, such as those of the type described in U.S. Pat. It is carried out at elevated temperatures close to the boiling point of.
この方法により、吸収および放散工程間（後者は通常ス
チームストリッピングによって行なわれる）での加熱お
よび冷却の際通常遭遇する熱損失は大いに回避されると
共に割高な溶液対溶液熱交換器が不要となる。This method largely avoids the heat losses normally encountered during heating and cooling between absorption and dissipation steps (the latter usually performed by steam stripping) and eliminates the need for expensive solution-to-solution heat exchangers. .
過去数年来、炭酸カリウムスクラッピング法の効率を高
めるため種種の添加剤が提案されている。Over the past few years, various additives have been proposed to increase the efficiency of the potassium carbonate scraping process.
吸収速度係数および溶液の平衡特性の両者を改良する効
果をもつかかる添加剤の一群はエタノールアミン類、特
にモノ−、ジーおよびトリエタノールアミンである（英
国特許第１０８４５２６号明細書参照）。A group of such additives which have the effect of improving both the absorption rate coefficient and the equilibrium properties of the solution are the ethanolamines, especially the mono-, di- and triethanolamines (see GB 1,084,526).
炭酸カリウム溶液の吸収効率の改良のため提案された他
の有機添加剤としては例えばアミンボレート（英国特許
第１０６３５１７号明細書参照）およびアミノ酸（例え
ば英国特許第７８６６６９号明細書参照）などがあげら
れる。Other organic additives that have been proposed to improve the absorption efficiency of potassium carbonate solutions include, for example, amine borates (see GB 1063517) and amino acids (see GB 786669). .
上述の有機添加剤の他に、吸収効率を改善するための炭
酸カリウム溶液用添加剤として多くの無機塩が提案され
ている。In addition to the organic additives mentioned above, many inorganic salts have been proposed as additives for potassium carbonate solutions to improve absorption efficiency.
例えば三酸化砒素（米国特許第３０３７８４４号明細書
参照）、亜セレン酸または亜テルル酸のアルカリ金属塩
（英国特許第７９１１５０号明細書参照）および弱無機
酸のアルカリ金属塩、例えば硼酸、バナジウム酸、亜砒
酸および亜アンチモン酸のカリウムおよびナトリウム塩
等（英国特許第８１９２１５号明細書参照）がある。For example, arsenic trioxide (see US Pat. No. 3,037,844), alkali metal salts of selenite or tellurite (see UK Patent No. 791,150) and alkali metal salts of weak inorganic acids, such as boric acid, vanadate, etc. , potassium and sodium salts of arsenous acid and antimonic acid (see British Patent No. 819,215).
腐食抑制のため炭酸カリウム溶液用添加剤としてバナジ
ウム塩を少量用いることも記載されている（米国特許第
３１８１９２９号明細書参照）。The use of small amounts of vanadium salts as additives for potassium carbonate solutions to inhibit corrosion has also been described (see US Pat. No. 3,181,929).
有機添加剤によっては、特に前記エタノールアミン類の
場合、全体的吸収効率に実質的改善がもたらされるが、
それらには、スクラッピング操作中酸化剤にさらされる
と酸化分解をうけるという制約がある。Some organic additives, particularly in the case of the ethanolamines mentioned above, can provide substantial improvements in overall absorption efficiency;
They have the limitation that they undergo oxidative degradation when exposed to oxidizing agents during scraping operations.
例えば、煙道ガスからＣＯ２を除去する場合、スクラッ
ピング溶液は該煙道ガス中に存在する実質量の酸素にさ
らされる。For example, when removing CO2 from a flue gas, the scraping solution is exposed to substantial amounts of oxygen present in the flue gas.
同じく、エチレンおよび酸素からのエチレンオキサイド
製造中に生じる再循環ガスからＣＯ２を除去する場合、
そのＣＯ２含有再循環ガスも実質量の酸素を含有する。Similarly, when removing CO2 from the recycle gas produced during the production of ethylene oxide from ethylene and oxygen,
The CO2-containing recycle gas also contains substantial amounts of oxygen.
この種ガスの酸素分は（特に吸収を高められた温度で行
なう場合）有機活性化剤と反応しまたそれを分解し、そ
のため吸収溶液は吸収効率を失いまた吸収溶液中に望ま
しくない副生物を生じやすくなる。The oxygen content of such gases (especially when absorption is carried out at elevated temperatures) reacts with and decomposes the organic activator, so that the absorption solution loses absorption efficiency and introduces undesirable by-products into the absorption solution. more likely to occur.
有機添加剤を含有する炭酸カリウム溶液により処理でき
るガスの種類が制限される他に、この種溶液はやはり酸
化分解をうけやすいために空気ストリッピングによって
は再生できないという別の制約をうける。In addition to being limited in the types of gases that can be treated with potassium carbonate solutions containing organic additives, another limitation is that these solutions are also susceptible to oxidative degradation and cannot be regenerated by air stripping.
多くの無機添加剤は上記制約をうけないが、それらは別
の短所がある。Although many inorganic additives do not suffer from the above limitations, they have other disadvantages.
例えば、炭酸カリウム溶液への砒素（ＡＳ２Ｏ３）の添
加は吸収効率を実質的に改善するが、前記砒素は例えば
１０重量％〜１５重量％といった比較的高濃度で用いね
ばならず、そのため作業員への災害および環境汚染問題
を生じる高毒性の溶液が生成する。For example, the addition of arsenic (AS2O3) to a potassium carbonate solution substantially improves absorption efficiency, but the arsenic must be used in relatively high concentrations, e.g. 10% to 15% by weight, so that Highly toxic solutions are produced which cause disasters and environmental pollution problems.
これまで提案された他の無機添加剤の多く（例えばバナ
ジウム塩および硼酸塩等）は、有機添加剤特にエタノー
ルアミン類を用いて得られる吸収効率の著しい改良に比
べ全体的吸収効率を相対的にほんのわずか改善するにす
ぎないことが判明した。Many of the other inorganic additives that have been proposed (e.g. vanadium salts and borates) provide relatively little overall absorption efficiency compared to the significant improvements in absorption efficiency obtained with organic additives, particularly ethanolamines. It was found that there was only a slight improvement in
本発明によりＣＯ２吸収に対する炭酸カリウム溶液の全
体的効率はスクラッピング溶液中に硼酸ナトリウムまた
はカリウムとバナジウムオキシ酸のナトリウムまたはカ
リウム塩との混合物を少量存在させることにより著しく
改良し得ることを見出した。It has been found in accordance with the present invention that the overall efficiency of potassium carbonate solutions for CO2 absorption can be significantly improved by the presence in the scraping solution of a small amount of a mixture of sodium or potassium borate and the sodium or potassium salt of vanadium oxyacid.
前記硼酸塩またはバナジウム塩単独では使用量とは無関
係に溶液の全体的吸収特性はいずれの場合も顕著に改良
されないが、これら二種の塩を適正な割合で組み合わせ
ると吸収効率が全体として著しく増加する。While the borate or vanadium salts alone do not in any case significantly improve the overall absorption properties of the solution, regardless of the amount used, the combination of these two salts in proper proportions significantly increases the overall absorption efficiency. do.
エタノールアミン類等の有機添加剤を用いた場合に得ら
れるとの同様の吸収効率を達成できると共にこれら無機
塩添加剤は含酸素ガスにさらされても酸化劣化をうけな
いという極めて重要な長所が新たに加えられる。In addition to achieving absorption efficiencies similar to those obtained using organic additives such as ethanolamines, these inorganic salt additives have the extremely important advantage of not being subject to oxidative degradation when exposed to oxygen-containing gases. New additions.
本発明の新規スクラッピング溶液は主成分として炭酸カ
リウム１５重量％〜４０重量％、好ましくは２０重量％
〜３５重量％に２ＣＯ３なる濃度で用いる。The novel scraping solution of the present invention has potassium carbonate as a main component of 15% to 40% by weight, preferably 20% by weight.
Used at a concentration of ~35% by weight 2CO3.
勿論ＣＯ２吸収に用いる実際の操作溶液は、炭酸カリウ
ムと重炭酸カリウムとの混合物であり、また上記重量％
値は全炭酸塩かに２ＣＯ３として存在するとの仮定に基
づいた炭酸塩濃度を表わす。Of course, the actual working solution used for CO2 absorption is a mixture of potassium carbonate and potassium bicarbonate, and the above weight %
Values represent carbonate concentrations based on the assumption that all carbonate is present as 2CO3.
例えばこの仮定に基づくと、１５重量％のに２ＣＯ３お
よび１４．４７重量％のＫＨＣＯ３を実際に含有する操
作溶液は２５％のに２ＣＯ３を含有するものとして定義
されることになろう。For example, based on this assumption, an operating solution that actually contains 15% by weight 2CO3 and 14.47% by weight KHCO3 would be defined as containing 25% 2CO3.
スクラッピング溶液中の硼酸ナトリウムまたはカリウム
の有効量は約２重量％〜１５重量％のＫＢＯ２当量の範
囲である。An effective amount of sodium or potassium borate in the scraping solution ranges from about 2% to 15% by weight KBO2 equivalents.
すなわち該溶液中の硼酸ナトリウムまたはカリウムの濃
度は該溶液の全重量に基づき２重量％〜１５重量％のＫ
ＢＯ２と化学的に等価である量にて存在すべきである。That is, the concentration of sodium or potassium borate in the solution is between 2% and 15% by weight of K based on the total weight of the solution.
It should be present in an amount that is chemically equivalent to BO2.
この硼酸塩の好ましい濃度は４重量％〜１０重量％のＫ
ＢＯ２当量である。The preferred concentration of this borate is between 4% and 10% K by weight.
It is BO2 equivalent.
硼酸ナトリウムまたはカリウム塩は種種の形態、例えば
メタ硼酸カリウム（Ｋ２Ｂ２Ｏ４）、四硼酸カリウム八
水和物（Ｋ２Ｂ４Ｏ７８Ｈ２Ｏ）、メタ硼酸ナトリウム
（Ｎａ２Ｂ２Ｏ４）、メタ硼酸ナトリウム四水和物（Ｎ
ａ２Ｂ２Ｏ４・４Ｈ２Ｏ）、四硼酸ナトリウム（Ｎａ２
Ｂ４Ｏ７）、四硼酸ナトリウム五水和物（Ｎａ２Ｂ４Ｏ
７・５Ｈ２Ｏ）、および四硼酸ナトリウム＋水和物（ボ
ラツクス、Ｎａ２Ｂ４Ｏ７・１０Ｈ２０）などとして存
在してもよい。Sodium or potassium borate salts are available in various forms, such as potassium metaborate (K2B2O4), potassium tetraborate octahydrate (K2B4O78H2O), sodium metaborate (Na2B2O4), sodium metaborate tetrahydrate (N
a2B2O4・4H2O), sodium tetraborate (Na2
B4O7), sodium tetraborate pentahydrate (Na2B4O
7.5H2O), and sodium tetraborate + hydrate (borax, Na2B4O7.10H20).
前記硼酸塩がスクラッピング溶液に溶解した場合に如何
なる形態で存在するのか明確には分らないが、該溶液中
の硼酸塩濃度を定義する目的で、該硼酸塩がＡＢＯ２（
ここでＡはカリウムまたはナトリウム原子である）とい
う単純な形態で存在するものと仮定し、また既に指摘し
たようにその濃度は、ＫＢＯ２当量として表現される。Although it is not clearly known in what form the borate exists when dissolved in the scraping solution, for the purpose of defining the borate concentration in the solution, the borate is ABO2 (
Here A is a potassium or sodium atom) and, as already pointed out, its concentration is expressed as KBO2 equivalents.
すなわち、４重量％のに２Ｂ２Ｏ４の溶液への添加は、
４重量％のＫＢＯ２当量を供与するものとして定義され
る。That is, the addition of 4% by weight of 2B2O4 to a solution is
Defined as providing 4% by weight of KBO2 equivalents.
同様に四硼酸カリウム八水和物（Ｋ２Ｂ４Ｏ７・８Ｈ２
Ｏ）およびＫＯＨ（Ｋ２Ｂ４Ｏ７・８Ｈ２０：ＫＯＨの
モル比は１：２である）の混合物の５．９８重量％の添
加は溶解状態では
に２Ｂ４Ｏ７・８Ｈ２Ｏ＋２ＫＯＨ→４ＫＢＯ２＋９Ｈ
２Ｏと仮定して４．０重量のＫＢＯ２当量を供与するも
のとして定義される。Similarly, potassium tetraborate octahydrate (K2B4O7・8H2
The addition of 5.98 wt.
Defined as providing 4.0 weight KBO2 equivalents assuming 2O.
同様に３．２２重量％のメタ硼酸ナトリウム、Ｎａ２Ｂ
２Ｏ４、の添加は４．０重量ＫＢＯ２当量を供与するも
のとして定義される。Similarly, 3.22% by weight of sodium metaborate, Na2B
The addition of 2O4 is defined as providing 4.0 weight KBO2 equivalents.
四硼酸ナトリウム五水和物、Ｎａ２Ｂ４Ｏ７・５Ｈ２Ｏ
１およびＮａ０Ｈ（Ｎａ２Ｂ４Ｏ７・５Ｈ２０：ＮａＯ
Ｈのモル比は１：２である）の混合物の４．５４重量％
の添加は４重量％のＫＢＯ２当量を供与するものとして
定義される（前記と同タイプの化学量論を仮定する）。Sodium tetraborate pentahydrate, Na2B4O7.5H2O
1 and Na0H (Na2B4O7・5H20:NaO
4.54% by weight of the mixture (the molar ratio of H is 1:2)
The addition of is defined as providing 4% by weight of KBO2 equivalents (assuming the same type of stoichiometry as above).
好ましい硼酸塩は硼酸カリウムである。The preferred borate is potassium borate.
炭酸カリウムスクラッピング溶液へ硼酸カリウムを添加
するための好都合な手順は単に硼酸を添加することであ
り、その場合該硼酸は次の式
２式％
に従って硼酸カリウムＫＢＯ２に変換されるものと仮定
される。A convenient procedure for adding potassium borate to a potassium carbonate scraping solution is to simply add boric acid, where it is assumed that the boric acid is converted to potassium borate KBO2 according to the following equation: .
この場合勿論溶液の炭酸カリウム含量は添加された硼酸
との反応により消費される分を補償するよう適正に調整
されねばならない。In this case, of course, the potassium carbonate content of the solution must be adjusted appropriately to compensate for the content consumed by the reaction with the added boric acid.
あるいはまた、そのＫＢＯ２は、例えば硼酸とに２ＣＯ
３との、または硼酸とＫＯＨとの混合物を調製するなど
して予め形成してもよい。Alternatively, the KBO2 can be combined with, for example, boric acid and 2CO
3 or by preparing a mixture of boric acid and KOH.
スクラッピング溶液中のバナジウムオキシ酸のナトリウ
ムまたはカリウム塩の有効量は約０．５重量％〜５重量
％のＶ２Ｏ５当量の範囲である。An effective amount of the sodium or potassium salt of vanadium oxyacid in the scraping solution ranges from about 0.5% to 5% by weight V2O5 equivalents.
すなわち、該溶液中のバナジウム塩の濃度は、該溶液の
全重量に基づき０．５重量％〜５重量％のＶ２Ｏ５に化
学的に等価な量であるべきである。That is, the concentration of vanadium salt in the solution should be an amount chemically equivalent to 0.5% to 5% V2O5 by weight based on the total weight of the solution.
このバナジウム塩の好ましい濃度は０．８重量％〜３重
量％のＶ２Ｏ５当量である。The preferred concentration of this vanadium salt is 0.8% to 3% by weight V2O5 equivalents.
これらバナジウムオキシ酸類は種種の形態で存在し、そ
の中で最も普通な形はメタバナジウム酸、ＨＶＯ３、お
よびピロバナジウム酸、Ｈ４Ｖ２Ｏ７である。These vanadium oxyacids exist in various forms, the most common of which are metavanadate, HVO3, and pyrovanadate, H4V2O7.
種種のバナジウムオキシ酸のナトリウムまたはカリウム
塩の任意のものを用いてもよく、特にバナジウム酸カリ
ウムまたはナトリウム、例えばメタバナジウム酸カリウ
ム（ＫＶＯ３）、ピロバナジウム酸カリウム（Ｋ４Ｖ２
Ｏ７）、メタバナジウム酸ナトリウム（ＮａＶＯ３）ま
たはピロバナジウム酸ナトリウム（Ｎａ４Ｖ２Ｏ７）等
を用いてもよい。Any of the various sodium or potassium salts of vanadium oxyacids may be used, especially potassium or sodium vanadates, such as potassium metavanadate (KVO3), potassium pyrovanadate (K4V2
O7), sodium metavanadate (NaVO3), sodium pyrovanadate (Na4V2O7), etc. may be used.
かかるナトリウムまたはカリウム塩は、炭酸カリウムス
クラッピング溶液にそのまま添加してもよく、あるいは
水性炭酸カリウムに可溶のバナジウム酸化物を添加する
（その際該酸化物と炭酸カリウムとの反応によりバナジ
ウム塩が生じる）ことにより系内に形成してもよい。Such sodium or potassium salts may be added neat to the potassium carbonate scraping solution, or a vanadium oxide soluble in the aqueous potassium carbonate may be added, with the reaction of the oxide with the potassium carbonate forming the vanadium salt. may be formed within the system by
例えばＶ２Ｏ５を炭酸カリウム溶液に添加するとバナジ
ウム酸カリウムが次の如く生じる。For example, when V2O5 is added to a potassium carbonate solution, potassium vanadate is produced as follows.
Ｋ２ＣＯ３＋Ｖ２Ｏ５→２ＫＶＣＯ３＋ＣＯ２更にまた
、前記バナジウム塩はバナジウム酸アンモニウムＮＨ４
ＶＯ３、を添加することによつも形成できる。K2CO3+V2O5→2KVCO3+CO2 Furthermore, the vanadium salt is ammonium vanadate NH4
It can also be formed by adding VO3.
その際、炭酸カリウムとの反応すなわち
に２ ＣＯ３＋ ２ ＮＨ４ＶＯ３→２ ＫＶＯ３＋（
ＮＨ４） ２ Ｃ０３によってバナジウム酸カリウムが
生じる。At that time, the reaction with potassium carbonate, that is, 2 CO3+ 2 NH4VO3 → 2 KVO3+ (
NH4) 2 C03 produces potassium vanadate.
操作条件下スクラッピング溶液中前記バナジウム塩の存
在する厳密な形態は明確には分らない。The exact form in which the vanadium salt is present in the scraping solution under operating conditions is not clearly known.
例えば、状況によってはそれらが数価の原子価形態、例
えば５価形態（例えばメタバナジウム酸カリウム、ＫＶ
Ｏ３）、または他のより低い原子価形態、例えば４価ま
たは３価形態または種種の原子価形態の混合として存在
するかもしれない証拠がある。For example, in some circumstances they may be present in multivalent forms, such as pentavalent forms (e.g. potassium metavanadate, KV
There is evidence that it may exist as O3), or other lower valence forms, such as a tetravalent or trivalent form or a mixture of different valence forms.
既に指摘したように、溶液中のバナジウム塩の濃度を定
義する目的で、該濃度はＶ２Ｏ５当量として表現される
。As already pointed out, for the purpose of defining the concentration of vanadium salt in solution, said concentration is expressed as V2O5 equivalents.
すなわち１重量％のＶ２Ｏ５の溶液への添加は１重量％
のＶ２Ｏ５当量を供与するものとして定義される。That is, the addition of 1% by weight of V2O5 to a solution is 1% by weight.
of V2O5 equivalents.
同様に１．５２％のＫＶＯ３または１．３４％のＮａＶ
Ｏ３の溶液への添加は１重量％の当価Ｖ２Ｏ５を供与す
るものとして定義される。Similarly 1.52% KVO3 or 1.34% NaV
Addition of O3 to the solution is defined as providing 1% by weight of equivalent V2O5.
上述の如く硼酸塩およびバナジウム塩の量を調節する他
に、これらの塩を適正な相対的割合で用いることも、著
しく高められた総括吸収効率という利点を得る上で必要
である。In addition to adjusting the amounts of borate and vanadium salts as described above, the use of these salts in the proper relative proportions is also necessary to obtain the benefit of significantly increased overall absorption efficiency.
スクラッピング溶液中のＫＢＯ２当量：Ｖ２Ｏ５当量の
重量比は少なくとも約１．５：１、好ましくは少なくと
も約２．５：１である。The weight ratio of KBO2 equivalents to V2O5 equivalents in the scraping solution is at least about 1.5:1, preferably at least about 2.5:1.
この重量比の上限は下限程臨界的でないがＫＢＯ２当量
：Ｖ２Ｏ５当量の重量比は一般に約１５：１を越えるべ
きでなく、また好ましくは２．５：１〜１０：１の範囲
にある。Although the upper limit of this weight ratio is not as critical as the lower limit, the weight ratio of KBO2 equivalents to V2O5 equivalents should generally not exceed about 15:1 and is preferably in the range of 2.5:1 to 10:1.
如上の通り、また後述する実施例において例示する通り
、炭酸カリウムスクラッピング溶液中の硼酸塩およびバ
ナジウム塩が同時に存在するとそれらが適正な割合で用
いられている限り、これらの塩を単独で用いた場合には
それぞれの塩それ自体では決して得られない総括吸収効
率が得られる。As mentioned above, and as exemplified in the Examples below, the simultaneous presence of borate and vanadium salts in the potassium carbonate scraping solution can be used alone as long as they are used in the proper proportions. In some cases, an overall absorption efficiency is obtained that could never be obtained with each salt on its own.
ＣＯ２液体吸収剤系における総括吸収効率は、吸収速度
係数および溶液単位容量あたりの総括ＣＯ２ピックアッ
プの両方の関数である。The overall absorption efficiency in a CO2 liquid absorbent system is a function of both the absorption rate coefficient and the overall CO2 pickup per unit volume of solution.
前記吸収速度係数は一般的用語でいうと、吸収速度の尺
度であり、また例えば単位推進力につき、溶液の単位容
量あたり毎時間に吸収されたＣＯ２の立方メートルとし
て表現してもよい。The absorption rate coefficient is, in general terms, a measure of the absorption rate and may be expressed, for example, as cubic meters of CO2 absorbed per hour per unit volume of solution per unit driving force.
ここで推進力とは勿論気相中のＣＯ２の分圧と溶液から
のＣＯ２の平衡逆圧との間の差である。The driving force here is of course the difference between the partial pressure of CO2 in the gas phase and the equilibrium back pressure of CO2 from the solution.
前記総括ＣＯ２ピックアップは１吸収サイクルごとに溶
液の単位容量あたり吸収され得るＣＯ２の最大量である
。The overall CO2 pickup is the maximum amount of CO2 that can be absorbed per unit volume of solution per absorption cycle.
この総括ＣＯ２ピックアップは大部分溶液の平衡特性の
関数すなわち溶液上のＣＯ２の平衡圧が該溶液中にロー
ディングするＣＯ２と共に変化する挙動である。This global CO2 pickup is largely a function of the equilibrium properties of the solution, ie, the behavior in which the equilibrium pressure of CO2 above the solution changes with the CO2 loading into the solution.
総括効率の高い吸収溶液においては、これらの要因（す
なわち吸収速度係数および総括ＣＯ２ピックアップ）の
いずれもが比較的高水準にある。In absorbent solutions with high overall efficiency, both of these factors (ie absorption rate coefficient and overall CO2 pickup) are at relatively high levels.
すなわち総括ＣＯ２ピックアップを犠牲にして吸収速度
係数を高めるかまたは吸収速度係数を犠牲にして総括ピ
ックアップを高めることは実際には総括吸収効率の低下
した溶液を生じかねない。That is, increasing the absorption rate coefficient at the expense of the overall CO2 pickup, or increasing the overall pickup at the expense of the absorption rate coefficient, may actually result in a solution with a reduced overall absorption efficiency.
本発明に至る研究過程において、炭酸カリウムスクラッ
ピング溶液への硼酸塩の添加は総括ＣＯ２ピックアップ
に対し好ましい効果を有し得るが、その総括ＣＯ２ピッ
クアップを実質的に改良するのに充分な量で用いると吸
収速度係数が悪影響をうけ、その結果総括吸収効率の効
果はほとんど得られないかまたは顕著でなくなることを
見出した。In the course of research leading to the present invention, it was determined that the addition of borate to the potassium carbonate scraping solution can have a positive effect on the overall CO2 pick-up, but used in amounts sufficient to substantially improve the overall CO2 pick-up. It was found that the absorption rate coefficient was adversely affected and, as a result, the effect of the overall absorption efficiency was hardly obtained or became insignificant.
更にまた炭酸カリウムスクラッピング溶液へのバナジウ
ム塩の添加は吸収速度係数に対し好ましい効果を有する
が、かかる添加は総括ピックアップに対し極めて好まし
くない効果を有しその結果総括吸収効率は屡屡実質的に
低下することを見出した。Furthermore, although the addition of vanadium salts to potassium carbonate scraping solutions has a positive effect on the absorption rate coefficient, such additions have a very unfavorable effect on the overall pickup, so that the overall absorption efficiency is often substantially reduced. I found out what to do.
これら不利な指摘にかかわらず、これら２種の塩の組み
合わせは、適正な量および適正な相対的割合で、炭酸カ
リウム溶液に添加されると、吸収速度係数および総括Ｃ
Ｏ２ピックアップの両方において所望の実質的改良をみ
るスクラッピング溶液を生成することを本発明により見
出した。Notwithstanding these adverse indications, the combination of these two salts, when added to a potassium carbonate solution in the proper amounts and in the proper relative proportions, will improve the absorption rate coefficient and the overall C
It has been found in accordance with the present invention to produce a scraping solution that exhibits the desired substantial improvement in both O2 pick-up.
個個の塩および適正な割合の該塩の組み合わせの相対的
挙動を次の実施例に例示する。The relative behavior of individual salts and combinations of the salts in appropriate proportions is illustrated in the following examples.
実施例
同一基準による結果を比較するために２５重量％の炭酸
カリウムを含有する水溶液を用いて次の実験を全て行な
った。EXAMPLE The following experiments were all carried out using an aqueous solution containing 25% by weight of potassium carbonate in order to compare the results on the same basis.
硼酸塩を用いる場合、それは硼酸をＫＯＨと反応させる
ことによって製造したＫＢＯ２として添加した。When borate was used, it was added as KBO2, which was made by reacting boric acid with KOH.
バナジウム塩を用いる場合、それはＫＶＯ３の形で存在
させ、またそのＫＶＯ３の重量は下記表において相当す
る％Ｖ２Ｏ５として表現する。If a vanadium salt is used, it is present in the form of KVO3 and the weight of KVO3 is expressed in the table below as the corresponding %V2O5.
例えば下記表に示した１％Ｖ２Ｏ５は１．５２％ＫＶＯ
３に相当する。For example, 1% V2O5 shown in the table below is 1.52% KVO
Corresponds to 3.
表示した組成の溶液を用いて、０．２８ｋｇ／ｃｍ２の
ＣＯ２に等しい平衡逆圧および１１０℃の温度における
溶液中へのＣＯ２の吸収速度を測定し、次表中「速度」
の欄に１気圧（１，０３ｋｇ／ｃｍ２）の推進力につき
溶液１１あたり毎時間に吸収されたＣＯ２の立方メート
ル数として表現した。Using a solution of the indicated composition, the absorption rate of CO2 into the solution at an equilibrium back pressure equal to 0.28 kg/cm2 of CO2 and a temperature of 110°C was measured, and the "rate" in the following table was determined.
It is expressed in the column as the number of cubic meters of CO2 absorbed per hour per solution 11 per 1 atm (1,03 kg/cm2) of driving force.
速度を０．２８ｋｇ／ｃｍ２の平衡逆圧にて測定したの
は、これが典型的な市販のＣＯ２スクラッピング装置に
おける吸収塔の塔頂近くに存在する典型的な条件だから
である。Velocities were measured at an equilibrium back pressure of 0.28 kg/cm2 as this is a typical condition that exists near the top of the absorption column in a typical commercial CO2 scraping unit.
推進力の最も低い吸収塔の塔頂部では、速度係数の高い
ことが特に重要である。A high velocity coefficient is particularly important at the top of the absorption tower where the driving force is lowest.
総括ＣＯ２ピックアップ（下記表において「ピックアッ
プ」の欄に示され、また溶液１立方メートルあたり吸収
されるＣＯ２の立方メートル数として表現される）は溶
液に対する平衡ＣＯ２分圧が０．２８ｋｇ／ｃｍ２およ
び１．７６ ｋｇ／ｃｍ２ （これらの値はＣＯ２除去
装置の商業的操作において遭遇する値の典型である）の
限界間を変化するに伴う平衡時溶液のＣＯ２含量の差と
して（立方メートル／立方メートル単位）１１０℃にて
各溶液について測定した。The overall CO2 pickup (shown in the "Pickup" column in the table below and expressed as cubic meters of CO2 absorbed per cubic meter of solution) is such that the equilibrium CO2 partial pressure for the solution is 0.28 kg/cm2 and 1.76 kg/cm2 (these values are typical of the values encountered in commercial operation of CO2 removal equipment) as the difference in the CO2 content of the solution at equilibrium (in cubic meters/cubic meter) to 110 °C. Measurements were made for each solution.
実験Ａ（２５重量％の炭酸カリウムのみを含有する溶液
）は種種溶液の挙動を比較するための標準的基準を与え
る。Experiment A (solution containing only 25% by weight potassium carbonate) provides a standard basis for comparing the behavior of different solutions.
下記の表は硼酸塩および（または）バナジウム塩−含有
溶液の各各について対照実験すなわち実験Ａに比べた速
度およびピックアップの変化率（％）を示す。The table below shows the percent change in speed and pickup for each of the borate and/or vanadium salt-containing solutions compared to the control experiment, Experiment A.
種種の量の硼酸塩のみを含有する溶液を対照実験Ａに対
比した実験Ａ−Ｄの結果を下記第１表に示す。The results of Experiments AD compared to Control Experiment A for solutions containing only borate in varying amounts are shown in Table 1 below.
第１表のデータに示される通り、５％までの量の硼酸塩
単独の添加は速度およびピックアップにおいて消極的な
または無視し得べき増加を生じたにすぎなかった。As shown by the data in Table 1, addition of borate alone in amounts up to 5% resulted in only negative or negligible increases in speed and pickup.
１０重量％の硼酸塩の添加はピックアップにおいて実質
的改良を生じるが速度の方は増加しないで悪影響をうけ
た。Addition of 10% by weight borate produced a substantial improvement in pick-up, but speed was adversely affected with no increase.
下記第２表ではバナジウム酸塩のみを１％〜５％の範囲
の量で添加した実験Ｅ〜Ｇの結果を対照実験Ａで得られ
た結果と対比する。Table 2 below compares the results of experiments E-G in which vanadate alone was added in amounts ranging from 1% to 5% with the results obtained in control experiment A.
第２表に示したように、バナジウム塩のみの添加は速度
係数を実質的に増大するがピックアップに極めて悪影響
を与えるという犠牲を伴う。As shown in Table 2, the addition of vanadium salt alone substantially increases the rate coefficient, but at the cost of having a very negative effect on pickup.
ピックアップが激しく低下する結果、溶液の総括吸収効
率は好影響よりはむしろ悪影響をうける。As a result of the sharp drop in pickup, the overall absorption efficiency of the solution is more adversely affected than positively.
下記第３表では、硼酸塩とバナジウム塩の両者を既に定
義した如き量および相対的割合で用いた実験Ｈ〜Ｏの結
果を、これらの塩のいずれをも含有していない対照実験
Ａと対比して示す。Table 3 below compares the results of experiments H to O, in which both borate and vanadium salts were used in the amounts and relative proportions as previously defined, with control experiment A, which did not contain either of these salts. and show.
第３表のデータに示したように、硼酸塩およびバナジウ
ム塩の両者を適正な量および割合で用いると速度係数お
よびＣＯ２ピックアップの両者における実質的増加が得
られ、これは他方を犠牲にした上での一方における増加
とは区別される。As shown in the data in Table 3, using both borates and vanadium salts in appropriate amounts and proportions results in substantial increases in both rate coefficient and CO2 pick-up, at the expense of the other. is distinguished from an increase on the one hand.
これらの要因の両方が同時に強化される結果、溶液同伴
能力（これは一般にピックアップに比例する）、速度係
数および総括速度（これは速度係数および総括ピックア
ップの両方に依存する）が同時に改良され、その結果、
個個の塩をもっては達し得ない総括効率の著しい改良が
得られる。The simultaneous enhancement of both of these factors results in simultaneous improvements in solution entrainment capacity (which is generally proportional to pick-up), rate factor and overall rate (which depends on both rate factor and overall pick-up), and its result,
Significant improvements in overall efficiency are obtained that cannot be achieved with individual salts.
第４表で、実験Ｐ〜Ｒは硼酸塩の重量割合をバナジウム
塩の重量割合よりも実質的に低く、あるいはほんの僅か
低くした溶液を用いて得られた結果を対照実験Ａで得ら
れた結果と対比して示す。In Table 4, experiments P to R were obtained using solutions in which the weight proportion of borate was substantially lower or only slightly lower than the weight proportion of vanadium salt compared to the results obtained in control experiment A. Shown in comparison with
第４表のデータに示した通り、これら２種の塩の併用（
ただし該２種の塩の相対的重量比は適正に選択されてい
ない）は速度係数および総括ピックアップの両方につい
て所望の同時増大をもたらすことができない。As shown in the data in Table 4, the combination of these two salts (
However, the relative weight ratios of the two salts are not properly chosen) cannot provide the desired simultaneous increase in both velocity coefficient and overall pickup.
当価ＫＢＯ２：当価Ｖ２Ｏ５の重量比がそれぞれ１：２
，２：３、および４：５である実験Ｐ、ＱおよびＨでは
、総括ピックアップの増大というよりはむしろ激しい減
退があり、その結果総括吸収効率が減退するかまたはほ
とんど有意な改良を受けない。The weight ratio of equivalent KBO2: equivalent V2O5 is 1:2, respectively.
.
本発明の新規吸収溶液は任意の所望の吸収サイクルにお
いて用いてもよい。The novel absorption solution of the present invention may be used in any desired absorption cycle.
勿論、大低の適用に対しては、本溶液は、吸収が吸収塔
で行なわれ（好ましくはＣＯ２−含有ガスを該溶液に対
し向流に移動させて行なう）かつ、ストリッピングが吸
収されたＣＯ２が該溶液からストリッピングされるスト
リッピング塔で行なわれそして該溶液が吸収および再生
段階の間を連続的に循環させられる通常の連続サソクル
で用いられるであろう。Of course, for large and low applications, the present solution can be prepared in such a way that the absorption takes place in an absorption column (preferably by moving the CO2-containing gas countercurrently to the solution) and the stripping takes place in an absorption column. A stripping column in which the CO2 is stripped from the solution may be used in a conventional continuous suspensor where the solution is continuously circulated between absorption and regeneration stages.
それら吸収およびストリッピング塔には勿論通常の充て
ん物またはプレートを備えて吸収およびストリッピング
操作中の緊密な気液接触を確実にさせる。The absorption and stripping columns are of course equipped with conventional packings or plates to ensure intimate gas-liquid contact during absorption and stripping operations.
一つの特に好ましいタイプのサイクルは米国特許第２８
８６４０５号明細書に記載されており、その場合少なく
とも大部分の吸収を大気圧より高い圧力下に溶液の大気
圧での沸点に近い温度にて行ない、またその溶液は大気
圧に近い減圧下にスチームストリッピングにより再生さ
れる。One particularly preferred type of cycle is U.S. Pat.
No. 86405, in which at least a major portion of the absorption is carried out at a pressure above atmospheric pressure and at a temperature close to the boiling point of the solution at atmospheric pressure, and the solution is placed under reduced pressure close to atmospheric pressure. Regenerated by steam stripping.
このサイクルでは、少なくとも大部分の吸収はストリッ
ピングとほぼ同温度で起り、その結果その操作は本来大
部分等温となり吸収および再生段階間における加熱およ
び冷却量が著しく低下する。In this cycle, at least most of the absorption occurs at about the same temperature as the stripping, so that the operation is largely isothermal in nature and significantly reduces the amount of heating and cooling between the absorption and regeneration stages.
このようなサイクルにおいては、米国特許第２８８６４
０５号明細書に指摘されているように、特に精製のガス
のＣ０２含量を例えば５００〜１５００ｐｐｍといった
低濃度にまで低下させたい場合には吸収塔の塔頂に導入
される溶液の比較的小部分を冷却することが屡屡望まし
い。In such a cycle, U.S. Pat.
As pointed out in No. 05, a relatively small portion of the solution introduced at the top of the absorption column is used, especially when it is desired to reduce the C02 content of the purified gas to low concentrations, e.g. 500-1500 ppm. It is often desirable to cool the
一方、適用によっては、吸収段階を再生段階よりも相当
低い温度で操作するのが望ましい場合があり、その場合
には熱損失を低く抑えるために吸収塔を出る比較的冷た
い溶液を、再生塔の塔底を出る熱溶液と熱交換させるの
が望ましいであろう。On the other hand, in some applications it may be desirable to operate the absorption stage at a significantly lower temperature than the regeneration stage, in which case the relatively cold solution leaving the absorption tower is transferred to the regeneration tower to keep heat losses low. It may be desirable to exchange heat with the hot solution exiting the bottom of the column.
スチームは吸収されたＣＯ２を溶液から除去するための
再生段階における好ましいストリッピング媒質であるが
、本発明の重要な利点は、使用する無機硼酸塩およびバ
ナジウム塩が酸化劣化に対して抵抗性があり、したがっ
て特定の適用に対する系の経済全体からストリッピング
媒質として空気が好適である場合には空気ストリッピン
グを用いてもよいということである。Although steam is the preferred stripping medium in the regeneration step to remove absorbed CO2 from solution, an important advantage of the present invention is that the inorganic borates and vanadium salts used are resistant to oxidative degradation. , thus air stripping may be used if the overall economics of the system for a particular application favor air as the stripping medium.
本発明のスクラッピング溶液を用いてもよい種種のサイ
クルについての上記の簡単な説明は、例示として意図さ
れたものであり、個個に述べたサイクルに加え、その他
のタイプの吸収サイクルを用いてもよい。The above brief description of the various types of cycles in which the scraping solution of the present invention may be used is intended to be illustrative, and in addition to the individually mentioned cycles, other types of absorption cycles may be used. Good too.
本発明の溶液を用いてもよいサイクルの他の例示的具体
例は、例えば米国特許第３５６３６９５号明細書、米国
特許第３５６３６９６号明細書および米国特許第３６４
２４３０号明細書に記載されている。Other exemplary embodiments of cycles in which solutions of the invention may be used are described, for example, in U.S. Pat. No. 3,563,695, U.S. Pat.
It is described in the specification of No. 2430.
本発明の新規スクラッピング溶液は主としてＣＯ２含有
ガスからのＣＯ２除去に有用であるが、そのＣＯ２含有
ガスは、該新規スクラッピング溶液により、全部または
一部除去し得る他の汚染物質を含有してもよい。The novel scraping solutions of the present invention are primarily useful for CO2 removal from CO2-containing gases that contain other contaminants that can be removed in whole or in part by the novel scraping solutions. Good too.
かようなガスは、例えばＨ２Ｓ、ＣＯ８、メルカプタン
類および有機スルフィド類を含有してもよい。Such gases may contain, for example, H2S, CO8, mercaptans and organic sulfides.
場合によっては、本発明の溶液は、大量のＨ２Ｓを含有
するガスのスクラッピングには全面的には適していない
かも知れない、というのも実質量のＨ２Ｓとバナジウム
塩との間で若干の反応が起こり、溶液中に不溶性沈殿を
生じまた該バナジウム塩が連続的に消費されるかも知れ
ないからである。In some cases, the solution of the present invention may not be completely suitable for the scraping of gases containing large amounts of H2S, since some reaction between the substantial amount of H2S and the vanadium salt may occur. may occur, resulting in insoluble precipitates in solution and the vanadium salt may be continuously consumed.
本発明のスクラッピング溶液は実質量の酸素をも含有す
るＣＯ２含有ガス混合物のスクラッピングに特に価値あ
るものとして適用されることになろう。The scraping solution of the present invention will find particular value in the scraping of CO2-containing gas mixtures that also contain substantial amounts of oxygen.
例えば炭酸カリウムスクラッピング溶液は、エチレンの
接触酸化によるエチレンオキサイドの製造において生じ
る再循環ガスからのＣＯ２除去に広く用いられている。For example, potassium carbonate scraping solutions are widely used for the removal of CO2 from recycle gas produced in the production of ethylene oxide by catalytic oxidation of ethylene.
この種循環ガスは約８％のＣＯ２の他に２％〜６％程度
の酸素を含有する。In addition to about 8% CO2, this type of circulating gas contains about 2% to 6% oxygen.
この種のガスを有機添加剤を含有する炭酸カリウム溶液
で処理する場合、特に熱吸収サイクルを用いる場合、エ
タノールアミン類等有機添加剤は迅速に酸化され、それ
らを不活性にしまた溶液中に望ましくない分解生成物を
生じる。When treating gases of this type with potassium carbonate solutions containing organic additives, especially when using a heat absorption cycle, organic additives such as ethanolamines are rapidly oxidized, rendering them inert and desirable in solution. No decomposition products are produced.
本発明により用いる硼酸塩とバナジウム塩との混合物は
かかる酸化劣化に対し抵抗性がありまた有機添加剤を用
いて得られる効率と同様総括吸収効率を著しく高める。The mixture of borates and vanadium salts used according to the invention is resistant to such oxidative degradation and significantly increases the overall absorption efficiency, similar to the efficiency obtained with organic additives.
本発明のスクラッピング溶液のもう一つの利点は全成分
が、有機添加剤を含有する溶液とは対照的に、零の揮発
度を有するということである。Another advantage of the inventive scraping solution is that all components have zero volatility, in contrast to solutions containing organic additives.
このため揮発による損失がなくなると共に精製ガスおよ
び（または）回収ＣＯ２の汚染が回避される。This eliminates losses due to volatilization and avoids contamination of purified gas and/or recovered CO2.
本発明の新規スクラッピング溶液のもう一つの特に価値
ある適用は、ＣＯ２回収のための含酸素煙道ガスの処理
である。Another particularly valuable application of the novel scraping solution of the present invention is the treatment of oxygenated flue gas for CO2 recovery.
典型的にはこの種のガスは１０％程度のＣＯ２と共に１
％〜５％の酸素を含有していることがある。Typically, this type of gas contains about 10% CO2
% to 5% oxygen.
硼酸塩およびバナジウム塩と共に本発明のスクラッピン
グ溶液にはその他の添加剤、例えば必要な場合消泡剤お
よび腐食防止剤などを用いてもよい。In addition to the borate and vanadium salts, other additives may be used in the scraping solution of the present invention, such as defoamers and corrosion inhibitors, if desired.
しかし一般的に、大多数の適用に対しては、定義された
濃度のバナジウム塩は優れた腐食防止を提供し、そのた
め、大部分のスクラッピング系にわたってカーボンスチ
ールを用いることが可能となり、また補助的な腐食防止
剤の使用は必要ではないであろう。However, in general, for the majority of applications, vanadium salts at defined concentrations provide excellent corrosion protection, allowing carbon steel to be used across most scraping systems, and as a supplement. The use of corrosion inhibitors may not be necessary.
Claims (1)
して２〜１５重量％のほう酸ナトリウムまたはカリウム
と、Ｖ２Ｏ５当量として０．５〜５重量％のバナジウム
オキシ酸ナトリウムまたはカリウムとを含有し、かつ上
記はう酸塩とバナジウムオキシ酸塩とはＫＢＯ２／Ｖ２
Ｏ５重量比が少なくとも１．５／１であるような割合で
あることを特徴とする、ガス混合物からＣＯ２を吸収す
るための水性溶液。It contains 115-40% by weight of potassium carbonate, 2-15% by weight of sodium or potassium borate as KBO2 equivalent, and 0.5-5% by weight of sodium or potassium vanadium oxylate as V2O5 equivalent, and Borate and vanadium oxylate are KBO2/V2
Aqueous solution for absorbing CO2 from gas mixtures, characterized in that the proportion is such that the O5 weight ratio is at least 1.5/1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28747572A | 1972-09-08 | 1972-09-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS4969572A JPS4969572A (en) | 1974-07-05 |
| JPS585087B2 true JPS585087B2 (en) | 1983-01-29 |
Family
ID=23103069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP48100380A Expired JPS585087B2 (en) | 1972-09-08 | 1973-09-07 | Gas congobutsukara CO2 obunrisuruhouhou oyobi |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS585087B2 (en) |
| BE (1) | BE804408A (en) |
| CA (1) | CA996334A (en) |
| DE (1) | DE2344499C2 (en) |
| FR (1) | FR2198776B1 (en) |
| GB (1) | GB1415036A (en) |
| IN (1) | IN141082B (en) |
| IT (1) | IT995217B (en) |
| NL (1) | NL183633C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2292510A1 (en) * | 1974-11-26 | 1976-06-25 | Eickmeyer Allen | Absorption desorption of acid gases from gas mixt. - using alkali metal borate soln. in presence of oxidising agent to retard corrosion of appts. |
| US4430312A (en) * | 1982-06-23 | 1984-02-07 | Eickmeyer Allen Garland | Removal of CO2 from gas mixtures |
| US5563282A (en) * | 1995-03-27 | 1996-10-08 | Union Carbide Chemicals & Plastics Technology Corporation | Thermal process for removal of contaminants from process streams |
| US6452027B1 (en) * | 2001-09-10 | 2002-09-17 | Scientific Design Company, Inc. | Heat recovery procedure |
| CN101066516B (en) * | 2007-06-06 | 2011-04-20 | 华东理工大学 | Decarbonizing solution comprising borate |
| ES2458224T3 (en) | 2010-05-18 | 2014-04-30 | Basf Se | Procedure for the removal of carbon dioxide (CO2) from a circulating gas system |
| US8814989B2 (en) | 2010-05-18 | 2014-08-26 | Basf Se | Process for removing carbon dioxide (CO2) from a cycle gas system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1142317A (en) * | 1966-02-01 | 1969-02-05 | Eickmeyer Allen Garland | Method for prevention of corrosion in carbon dioxide removal systems |
-
1973
- 1973-08-20 GB GB3933073A patent/GB1415036A/en not_active Expired
- 1973-08-21 IN IN1924/CAL/1973A patent/IN141082B/en unknown
- 1973-08-24 IT IT28208/73A patent/IT995217B/en active
- 1973-08-31 FR FR7331610A patent/FR2198776B1/fr not_active Expired
- 1973-09-03 BE BE135278A patent/BE804408A/en not_active IP Right Cessation
- 1973-09-04 DE DE2344499A patent/DE2344499C2/en not_active Expired
- 1973-09-05 CA CA180,319A patent/CA996334A/en not_active Expired
- 1973-09-07 NL NLAANVRAGE7312367,A patent/NL183633C/en not_active IP Right Cessation
- 1973-09-07 JP JP48100380A patent/JPS585087B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1415036A (en) | 1975-11-26 |
| DE2344499A1 (en) | 1974-03-14 |
| FR2198776A1 (en) | 1974-04-05 |
| BE804408A (en) | 1974-03-04 |
| DE2344499C2 (en) | 1986-09-18 |
| CA996334A (en) | 1976-09-07 |
| FR2198776B1 (en) | 1980-07-04 |
| IN141082B (en) | 1977-01-15 |
| NL183633C (en) | 1988-12-16 |
| NL7312367A (en) | 1974-03-12 |
| IT995217B (en) | 1975-11-10 |
| JPS4969572A (en) | 1974-07-05 |
| AU5952673A (en) | 1975-02-27 |
| NL183633B (en) | 1988-07-18 |
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