WO2009110586A1 - Aqueous solution and method for absorbing and collecting carbon dioxide in gas efficiently - Google Patents
Aqueous solution and method for absorbing and collecting carbon dioxide in gas efficiently Download PDFInfo
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- WO2009110586A1 WO2009110586A1 PCT/JP2009/054260 JP2009054260W WO2009110586A1 WO 2009110586 A1 WO2009110586 A1 WO 2009110586A1 JP 2009054260 W JP2009054260 W JP 2009054260W WO 2009110586 A1 WO2009110586 A1 WO 2009110586A1
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- Prior art keywords
- carbon dioxide
- aqueous solution
- group
- absorption
- reaction
- Prior art date
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 287
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 143
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 142
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims description 30
- -1 tertiary amine compound Chemical group 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 31
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 238000010521 absorption reaction Methods 0.000 claims description 64
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 20
- 238000011084 recovery Methods 0.000 claims description 20
- KZTWONRVIPPDKH-UHFFFAOYSA-N 2-(piperidin-1-yl)ethanol Chemical compound OCCN1CCCCC1 KZTWONRVIPPDKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 150000004885 piperazines Chemical class 0.000 claims description 5
- HXXJMMLIEYAFOZ-UHFFFAOYSA-N (1-methylpiperidin-2-yl)methanol Chemical compound CN1CCCCC1CO HXXJMMLIEYAFOZ-UHFFFAOYSA-N 0.000 claims description 4
- UGXQXVDTGJCQHR-UHFFFAOYSA-N (1-methylpiperidin-3-yl)methanol Chemical compound CN1CCCC(CO)C1 UGXQXVDTGJCQHR-UHFFFAOYSA-N 0.000 claims description 4
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims description 4
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims description 4
- QDCVURQLJNIQBY-UHFFFAOYSA-N (1-ethylpiperidin-2-yl)methanol Chemical compound CCN1CCCCC1CO QDCVURQLJNIQBY-UHFFFAOYSA-N 0.000 claims description 3
- UFFXQKBVALLYQW-UHFFFAOYSA-N (1-ethylpiperidin-3-yl)methanol Chemical compound CCN1CCCC(CO)C1 UFFXQKBVALLYQW-UHFFFAOYSA-N 0.000 claims description 3
- IFNWESYYDINUHV-UHFFFAOYSA-N 2,6-dimethylpiperazine Chemical compound CC1CNCC(C)N1 IFNWESYYDINUHV-UHFFFAOYSA-N 0.000 claims description 3
- XFBHCXHXXLBHOM-UHFFFAOYSA-N 2-(1-ethylpiperidin-2-yl)ethanol Chemical compound CCN1CCCCC1CCO XFBHCXHXXLBHOM-UHFFFAOYSA-N 0.000 claims description 3
- OVMRRCXDBKEQIU-UHFFFAOYSA-N 2-(1-methylpiperidin-2-yl)ethanol Chemical compound CN1CCCCC1CCO OVMRRCXDBKEQIU-UHFFFAOYSA-N 0.000 claims description 3
- RILLZYSZSDGYGV-UHFFFAOYSA-N 2-(propan-2-ylamino)ethanol Chemical compound CC(C)NCCO RILLZYSZSDGYGV-UHFFFAOYSA-N 0.000 claims description 3
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 3
- ZMJQROKRSPSLFH-UHFFFAOYSA-N 3-pyrrolidin-1-ylpropan-1-ol Chemical compound OCCCN1CCCC1 ZMJQROKRSPSLFH-UHFFFAOYSA-N 0.000 claims description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 3
- XBRDBODLCHKXHI-UHFFFAOYSA-N epolamine Chemical compound OCCN1CCCC1 XBRDBODLCHKXHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 51
- 150000001412 amines Chemical class 0.000 description 25
- 238000003795 desorption Methods 0.000 description 23
- 150000003512 tertiary amines Chemical class 0.000 description 17
- 239000007788 liquid Substances 0.000 description 11
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 10
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- KJZLJGZZDNGGCA-UHFFFAOYSA-N (1-methylpiperidin-4-yl)methanol Chemical compound CN1CCC(CO)CC1 KJZLJGZZDNGGCA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 2
- 102100035605 Cas scaffolding protein family member 4 Human genes 0.000 description 2
- 102100024482 Cell division cycle-associated protein 4 Human genes 0.000 description 2
- 101100383112 Homo sapiens CDCA4 gene Proteins 0.000 description 2
- 101000947106 Homo sapiens Cas scaffolding protein family member 4 Proteins 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- KQDIGHIVUUADBZ-PEDHHIEDSA-N pentigetide Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CO)C(=O)N[C@@H](CC(O)=O)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CCCNC(N)=N)C(O)=O KQDIGHIVUUADBZ-PEDHHIEDSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006203 ethylation Effects 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RJUAEBLXGFKZMS-UHFFFAOYSA-N piperidin-1-ylmethanol Chemical compound OCN1CCCCC1 RJUAEBLXGFKZMS-UHFFFAOYSA-N 0.000 description 1
- PRAYXGYYVXRDDW-UHFFFAOYSA-N piperidin-2-ylmethanol Chemical compound OCC1CCCCN1 PRAYXGYYVXRDDW-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011282 treatment Methods 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
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
Definitions
- the present invention absorbs carbon dioxide (CO 2 ) contained in a gas using an aqueous solution for carbon dioxide absorption and recovery, and subsequently desorbs carbon dioxide from the carbon dioxide absorption and recovery aqueous solution in which carbon dioxide is absorbed.
- the present invention relates to an aqueous solution and a method for recovering separately.
- Sources of carbon dioxide include coal, heavy oil, natural gas and other thermal power plants, factory boilers or kilns in cement plants, blast furnace blast furnaces that reduce iron oxide with coke, gasoline, heavy oil,
- transportation equipment such as automobiles, ships, and aircraft that use light oil as fuel. Of these, those other than transportation equipment are fixed facilities, and are expected to be easy to implement measures to reduce carbon dioxide emissions.
- examples of the alkanolamine include monoethanolamine (hereinafter sometimes referred to as MEA), diethanolamine (hereinafter sometimes referred to as DEA), triethanolamine (hereinafter sometimes referred to as TEA), methyldiethanolamine ( Hereinafter, it may be indicated as MDEA), diisopropanolamine (DIPA), diglycolamine (DGA), etc., but MEA is usually used.
- MEA monoethanolamine
- DEA diethanolamine
- TEA triethanolamine
- MDEA diisopropanolamine
- DGA diglycolamine
- the absorbing solution when an aqueous solution of these alkanolamines is used as the absorbing solution, the corrosiveness of the device material is high, and therefore it is necessary to use expensive corrosion-resistant steel for the device or to reduce the amine concentration in the absorbing solution. Further, since the absorbed carbon dioxide is difficult to desorb, it was necessary to desorb and recover by heating the desorption temperature to a high temperature of 120 ° C. In addition, the energy required for desorbing carbon dioxide from the absorbing solution is also high at 85 kJ / mol CO 2 . For example, in order to collect carbon dioxide at a power plant using this method, extra energy equivalent to 20% of the power generation amount is required. In an era where reduction of carbon dioxide generation, energy saving and resource saving are required, this high energy consumption is a major factor that impedes the practical use of carbon dioxide absorption and recovery equipment.
- Patent Document 1 a so-called hindered amine aqueous solution having a steric hindrance such as an alkyl group around an amino group is brought into contact with combustion exhaust gas under atmospheric pressure, and carbon dioxide is absorbed in the aqueous solution.
- a method for removing carbon dioxide is described.
- Patent Document 1 examples of 2-methylaminoethanol (hereinafter sometimes referred to as MAE) and 2-ethylaminoethanol (hereinafter sometimes referred to as EAE) as hindered amines are described, and MAE and EAE are described. Is described as being preferred for carbon dioxide absorption.
- MAE 2-methylaminoethanol
- EAE 2-ethylaminoethanol
- Patent Document 2 describes a carbon dioxide recovery method including a step of bringing an aqueous amine solution and a mixed gas into contact with each other to absorb carbon dioxide and a step of desorbing carbon dioxide from the aqueous solution.
- Patent Document 2 discloses, as an aqueous amine solution, a compound containing a secondary amino group bonded to a secondary or tertiary carbon or a primary amino group bonded to a tertiary carbon, such as 2-methylpiperazine (hereinafter referred to as 2MPZ). 2) -amino-2-methyl-1-propanol (hereinafter sometimes referred to as AMP) and the like.
- 2MPZ 2-methylpiperazine
- AMP -amino-2-methyl-1-propanol
- Patent Document 3 exemplifies a mixture of amine compounds having two or more primary, secondary, and tertiary nitrogens in the molecule as components of the absorbing solution.
- Patent Document 4 proposes secondary cyclic amines substituted with a hydroxyl group or a hydroxyalkyl group as an amine component constituting the absorbing solution.
- the substitution position is a carbon atom, Direct substitution compounds on the group are not included.
- the removal of carbon dioxide from the exhaust gas that is, the absorption process of carbon dioxide into the aqueous solution and the desorption process of carbon dioxide from the aqueous solution that absorbed carbon dioxide are performed with high efficiency.
- the recovery energy consumed for carbon dioxide recovery is required to be low, and it is important to develop an absorbing solution that can achieve this.
- the present invention provides an aqueous solution and method for recovering high purity carbon dioxide with low energy consumption in order to efficiently absorb and recover carbon dioxide in gas.
- an aqueous solution containing at least one tertiary amine compound that has a low heat of reaction between carbon dioxide and an amine and the use of the aqueous solution reduces the overall energy required for carbon dioxide absorption and recovery, resulting in high purity. It aims at providing the method of collect
- the present inventors have found that the heat of reaction of the tertiary amine compound represented by the general formula [1] with carbon dioxide is lower than that of the conventional tertiary amine. I found.
- the reaction heat, reaction rate, absorption amount, and desorption performance that characterize the performance of amines used for absorption are in a trade-off relationship.
- amines with low reaction heat have absorption rates and absorption amounts.
- the tertiary amine according to the present invention is surprisingly small in performance degradation and has unprecedented characteristics, and is excellent without being bound by the conventional trade-off relationship. It turns out that it has performance.
- This reduction in the heat of reaction between carbon dioxide and the amine compound results in a reduction in the thermal energy applied during the desorption of carbon dioxide, enabling a reduction in the overall recovery energy in carbon dioxide recovery and solving the problems of the present invention. is there.
- the aqueous solution containing the amine of the present invention as a part of the aqueous solution has an absorption rate and a desorption rate required for industrially and economically recovering carbon dioxide, and the overall recovery energy is smaller than before. It has been found that it has performance. As a result of further research based on this knowledge, the present invention has been completed.
- Item 1 An aqueous solution for absorbing and recovering carbon dioxide from a gas containing carbon dioxide, wherein the aqueous solution contains at least one tertiary amine compound represented by the general formula [1].
- n is selected from 1 or 2
- R 1 represents an alkyl group or a hydroxyalkyl group
- R 2 is a 2-position or a 3-position
- R 2 represents hydrogen, an alkyl group or a hydroxyalkyl group
- At least one of R 1 and R 2 represents a hydroxyalkyl group.
- the tertiary amine compound of the general formula [1] is 1-methyl-2-piperidinemethanol, 1-methyl-2-piperidineethanol, 1-methyl-3-piperidinemethanol, 1-ethyl-2-piperidinemethanol, 1- From the group consisting of ethyl-3-piperidinemethanol, 1-ethyl-2-piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) piperidine and 1- (3-hydroxypropyl) pyrrolidine 2.
- Item 4. Item 4. The aqueous solution according to any one of Items 1 to 3, further comprising at least one selected from the group consisting of alkanolamines and piperazines.
- Item 5. Item 5. The aqueous solution according to Item 4, wherein the alkanolamine is at least one selected from the group consisting of 2- (isopropylamino) ethanol, 2- (ethylamino) ethanol, and 2-amino-2-methyl-1-propanol.
- Item 6. Item 6.
- Item 7. (1) A step of bringing the aqueous solution into contact with the aqueous solution according to any one of Items 1 to 6 to absorb carbon dioxide, and (2) heating the aqueous solution having absorbed carbon dioxide obtained in (1) above. Desorbing and recovering carbon dioxide, Carbon dioxide absorption and recovery method comprising:
- the method for separating and recovering carbon dioxide using the carbon dioxide absorbing liquid of the present invention has a high purity by absorbing and desorbing carbon dioxide in the gas with a lower energy consumption compared to known aqueous solutions for absorbing carbon dioxide. Of carbon dioxide can be recovered.
- the decrease in absorption rate which has been accompanied by the use of a tertiary amine, is small, thereby reducing the overall recovery heat when recovering carbon dioxide and improving the equipment efficiency.
- it is possible to reduce the recovered energy per unit weight of carbon dioxide which leads to the reduction of the recovery cost that is currently an issue.
- This also makes it possible to reduce the size of the absorption tower, the desorption tower, and the devices associated therewith for recovering and desorbing carbon dioxide, thereby reducing energy loss and reducing the construction cost.
- Aqueous solution for absorbing and recovering carbon dioxide is characterized by containing at least one tertiary amine compound represented by the general formula [1].
- R 1 in the general formula [1] includes an alkyl group or a hydroxyalkyl group.
- R 1 is an alkyl group, it preferably has 1 to 3 carbon atoms, and when it is a hydroxyalkyl group, it has a carbon number. Two or three are preferred. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hydroxyethyl group, a hydroxypropyl group, and the like, and a methyl group, an ethyl group, a hydroxyethyl group, and a hydroxypropyl group are preferably selected.
- R 2 in the general formula [1] includes hydrogen, an alkyl group, or a hydroxyalkyl group, and the alkyl group and the hydroxyalkyl group preferably have 1 to 3 carbon atoms.
- Specific examples include hydrogen, methyl group, ethyl group, propyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc., preferably hydrogen, methyl group, ethyl group, hydroxymethyl group, hydroxyethyl group And a hydroxypropyl group are selected.
- At least one of R 1 and R 2 in the general formula [1] is a hydroxyalkyl group.
- R 1 and R 2 when R 1 is a hydroxyalkyl group (preferably having 2 or 3 carbon atoms), R 2 is preferably hydrogen or an alkyl group (preferably having 1 to 3 carbon atoms) When 1 is an alkyl group (preferably having 1 to 3 carbon atoms), R 2 is preferably a combination of selecting a hydroxyalkyl group (preferably having 1 to 3 carbon atoms). For the substitution position of R 2 , substitution at the 2- and 3-position is selected.
- R 1 is an alkyl group
- 1-methyl-2-piperidinemethanol hereinafter also referred to as M2PPM
- 1-methyl-2-piperidineethanol hereinafter also referred to as M2PPE
- E2PPM 1-methyl-3-piperidinemethanol
- E3PPM 1-ethyl-3-piperidinemethanol
- R 2 is hydrogen
- 1- (2 hydroxyethyl) -pyrrolidine hereinafter also referred to as HEPL
- 1- (2 hydroxyethyl) -piperidine hereinafter also referred to as HEPP
- 1 -(3-Hydroxypropyl) pyrrolidine and the like are selected.
- tertiary amine compounds in the present application are known and can be obtained as reagents, but the production methods are described below for typical compounds.
- R 1 is an alkyl group and R 2 is a hydroxyalkyl group, for example, 1-methyl-piperidinemethanol
- R 2 is a hydroxyalkyl group
- 1-methyl-piperidinemethanol it can be obtained by methylating a known 2-piperidinemethanol with methanol (European Journal of Inorganic Chemistry (3), 524-529; 2004).
- reaction that absorbs carbon dioxide is an exothermic reaction
- reaction that desorbs the opposite carbon dioxide is an endothermic reaction
- reaction heat is used as meaning heat generated when absorbing carbon dioxide or heat absorbed from the outside when desorbing carbon dioxide.
- the aforementioned MEA which is often used for carbon dioxide absorption, is a typical primary amine, and the reaction heat of carbon dioxide is about 85 kJ / mole CO 2 , but it is a typical example of a tertiary amine.
- the heat of reaction is about 65 kJ / mol CO 2, which is a very low value.
- the MDEA is as small as 0.2, and as described above, there is a trade-off relationship that a reduction in reaction heat leads to a decrease in reaction rate.
- the tertiary amine according to the present invention has a characteristic that not only the heat of reaction is lower than that of the normal amine MDEA but also that the accompanying rate decrease is not observed at low heat of reaction. It shows different performance.
- the absorption rate of MDEA (concentration of 3 ⁇ mol / L) is 0.8 ⁇ g / L / min
- 1-methyl 2-piperidinemethanol according to the present invention is 2.7 ⁇ g / L / min at the same concentration. showed that. This is also considered to be a manifestation of the steric effect that the compound of the present invention shows in the course of the reaction.
- the aqueous solution based on the present invention is prepared by mixing the tertiary amine represented by the general formula [1] with at least one selected from the group of alkanolamines and piperazines to adjust the performance of the entire aqueous solution. Also good.
- the use of the tertiary amine compound represented by the general formula [1] can reduce the heat of reaction as an aqueous solution and improve the reaction rate, and the overall energy associated with the absorption and recovery of carbon dioxide. Consumption will be reduced and economic effects will be exerted.
- Alkanolamines and piperazines are listed as constituents of the aqueous solution other than the tertiary amine compound represented by the general formula [1].
- alkanolamines primary, secondary and tertiary amines are selected.
- 2- (isopropylamino) ethanol hereinafter sometimes referred to as IPAE
- 2- (ethylamino) ethanol 2-amino-2-methyl-1-propanol are preferably selected.
- Piperazines include piperazine alone and those having an alkyl substitution in the cyclic part of piperazine, preferably piperazine (hereinafter sometimes referred to as PZ), 2-methylpiperazine, and 2,6- Dimethyl piperazine is selected. These function as a reaction activator upon absorption of carbon dioxide.
- the content of the tertiary amine represented by the general formula [1] in the aqueous solution of the present invention is usually 5 to 45% by weight, preferably 8 to 40% by weight, more preferably 10 to 35% by weight.
- the content of alkanolamines in the aqueous solution of the present invention is usually 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 15 to 40% by weight.
- the content of piperazine in the aqueous solution of the present invention is usually 1 to 15% by weight, preferably 2 to 10% by weight, more preferably 3 to 9% by weight.
- an optimal composition is selected in consideration of the reaction heat, absorption amount, absorption rate, and desorption performance of each amine.
- Increasing the composition ratio of the tertiary amine according to the present invention has the effect of reducing the heat of reaction of the entire aqueous solution, but practically performance design including absorption amount, desorption amount, etc. is necessary. Make adjustments and set the ratio of aqueous solution composition.
- the content of the total amine compound in the aqueous solution according to the present invention is selected to be 20 to 65% by weight, preferably 30 to 60% by weight.
- the higher the concentration of the amine component the greater the amount of carbon dioxide absorbed, the amount of desorption, and the rate of desorption per unit liquid volume, which is desirable in terms of energy consumption and the size and efficiency of plant equipment. If it exceeds 70%, the amount of carbon dioxide absorbed decreases because the effect of water as an activator decreases. Also, problems such as foaming or emulsification may occur when the amine component is not mixed with water uniformly, the viscosity increases, or when the pH of the liquid is lowered by absorbing carbon dioxide.
- Carbon dioxide absorption step The carbon dioxide absorption and recovery method of the present invention includes a step of bringing a carbon dioxide-containing gas into contact with the carbon dioxide absorption and recovery aqueous solution to cause the aqueous solution to absorb carbon dioxide.
- Gases containing carbon dioxide include, for example, thermal power plants fueled with heavy oil, natural gas, etc., kilns at manufacturing plants or kilns at cement plants, blast furnaces at ironworks that reduce iron oxide with coke, carbon in pig iron Exhaust gas from a converter in the same ironworks where the steel is burned to produce steel, and the carbon dioxide concentration in the gas is usually about 5 to 30% by volume, particularly about 10 to 25% by volume. In such a carbon dioxide concentration range, the effects of the present invention are suitably exhibited.
- the gas containing carbon dioxide may contain gas such as water vapor, CO, H 2 S, and COS in addition to carbon dioxide.
- the method for bringing a gas containing carbon dioxide into contact with the aqueous solution is not particularly limited.
- a method of bubbling and absorbing a gas containing carbon dioxide in the aqueous solution a method of dropping the aqueous solution into a gas stream containing carbon dioxide (a spraying or spraying method), or a magnetic or metal mesh
- the temperature when the aqueous solution of the present invention and a gas containing carbon dioxide are brought into contact with each other to absorb carbon dioxide is preferably in the range of 30 to 70 ° C.
- the pressure during carbon dioxide absorption is usually about atmospheric pressure. Although it is possible to pressurize to a higher pressure in order to enhance the absorption performance, it is preferable to carry out under atmospheric pressure in order to suppress energy consumption required for compression.
- Carbon dioxide desorption step The method of the present invention includes a step of heating and recovering the carbon dioxide-absorbed aqueous solution obtained in the carbon dioxide absorption step of (1) above.
- a method of desorbing carbon dioxide from an aqueous solution that has absorbed carbon dioxide and recovering pure or high-concentration carbon dioxide a method of heating the aqueous solution and removing it by bubbling in a kettle as in distillation, a plate tower, a spray Examples include a method in which a liquid interface is widened and heated in a tower and a desorption tower containing a magnetic or metal mesh filler. Thereby, carbon dioxide is liberated and released from carbamate and bicarbonate.
- the temperature at the time of desorption of carbon dioxide after absorption is exemplified by a range of 90 to 130 ° C.
- the pressure during carbon dioxide desorption is usually about atmospheric pressure.
- the pressure can be reduced to a lower pressure in order to enhance the desorption performance, it is preferably performed under atmospheric pressure in order to suppress energy consumption required for the pressure reduction.
- the aqueous solution from which carbon dioxide has been desorbed is sent again to the carbon dioxide absorption process and recycled. During this time, the heat applied in the carbon dioxide desorption process is effectively used to increase the temperature of the aqueous solution by heat exchange with the aqueous solution in the circulation process, thereby reducing the energy of the entire recovery process.
- the purity of carbon dioxide recovered in this way is usually extremely high, about 95 to 99.9% by volume.
- This pure carbon dioxide or high-concentration carbon dioxide is used as a chemical, a raw material for synthesizing a high-molecular substance, or a cooling agent for freezing food.
- % means “% by weight”.
- M2PPM, MDEA, IPAE and PZ all use reagents from Tokyo Chemical Industry Co., Ltd., and E3PPM and 1-methyl-4-piperidinemethanol (M4PPM) According to the method described in the examples, the corresponding piperidine methanol was synthesized by ethylation or methylation.
- the saturated carbon dioxide absorption is a value obtained by measuring the amount of inorganic carbon in the aqueous solution with a gas chromatographic total organic carbon meter, and the carbon dioxide absorption rate is carbon dioxide that is 1/2 of the saturated absorption. It is a value measured using an infrared carbon dioxide meter at the time of absorbing.
- Example 1 A glass gas absorption bottle is immersed in a constant-temperature water bath set to a temperature of 40 ° C, and 50 ml of an aqueous solution containing 22% by weight of M2PPM, 25% by weight of IPAE and 3% by weight of PZ is placed in this bottle. Filled. A mixed gas containing 20% by volume of carbon dioxide and 80% by volume of N 2 at a pressure of 0.7 L / min is dispersed in a foam form through this glass filter with a coarseness of 100 ⁇ m and a diameter of 13 mm. And absorbed.
- the carbon dioxide concentration in the gas at the aqueous solution inlet and the aqueous solution outlet is continuously measured with an infrared carbon dioxide meter (HORIBA GAS ANALYZER VA-3000). Was measured. If necessary, the amount of inorganic carbon in the aqueous solution was measured with a gas chromatographic total organic carbon meter (SHIMADZU-TOC-VCSH) and compared with the value calculated from an infrared carbon dioxide meter.
- the saturated absorption amount was the amount at the time when the carbon dioxide concentration at the outlet of the aqueous solution coincided with the carbon dioxide concentration at the inlet.
- the absorption rate was compared with the absorption rate at the time when 1/2 of the saturated absorption amount was absorbed.
- the saturated absorption of carbon dioxide was 148 g / L, and the absorption rate at half absorption of the saturated absorption was 5.0 g / L / min.
- the liquid temperature was raised to 70 ° C. in several minutes in the same gas stream, and the amount of carbon dioxide desorbed from the liquid was measured. As a result, it was 56 g / L.
- the reaction heat measured by the method shown in Test Example 1 was 72 kJ / mol CO 2 .
- Examples 2-6 Using the same apparatus as in Example 1, under the same conditions, heat of reaction, saturated absorption, absorption rate at the time of carbon dioxide absorption using an aqueous solution containing M2PPM, E3PPM, HEPP, HEPL, IPAE, and PZ at the concentrations shown in Table 1 And the amount of carbon dioxide desorption was measured. The obtained results are shown in Table 1.
- [I] represents the composition of the tertiary amine according to the present invention
- [II] represents the alkanolamine
- [III] represents the piperazine composition name and weight%.
- the tertiary amine according to the present invention has not only the heat of reaction but also the absorption reaction rate and the saturated absorption amount as compared with MDEA, which is a typical tertiary amine conventionally known. The specific high performance of these amines was confirmed.
- the tertiary amine is an aqueous solution containing the tertiary amine as a component [I], an alkanolamine as a component [II], and a piperazine as a component [III].
- Comparative Example 3 shows the absorption performance when MDEA, which has been conventionally used industrially as a tertiary amine, is included. If 72 kJ / mol CO 2 of Example 1, are now industrially of MEA used 85 kJ / molCO 2 much lower than, the reduction of energy recovered carbon dioxide is an object of the present invention is made .
- the rate at the time of carbon dioxide absorption is higher than that of Comparative Example 3 in which Examples 4, 5, and 6 contain MDEA, which is a conventional representative tertiary amine, as a component of [I]. It was confirmed that this is a great advantage.
- Test example 1 The reaction heat of carbon dioxide absorption was measured using a differential thermal reaction calorimeter (SETARAM, DRC) consisting of a glass reaction tank and a reference tank of the same shape installed in a thermostat. Each of the reaction tank and the reference tank is filled with 150 mL of the aqueous solution of Example 2, and 40 ° C. constant temperature water is circulated in the jacket portion of the tank. In this state, 100% carbon dioxide gas was blown into the reaction vessel aqueous solution at 200 ml / min, and the temperature rise of the liquid was continuously recorded with a temperature recorder until the carbon dioxide absorption was completed, and measured in advance. The reaction heat was calculated using the overall heat transfer coefficient between the reaction tank and the jacket water. Reaction heat resulting carbon dioxide absorption was 58 kJ / molCO 2.
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Abstract
Disclosed is an aqueous solution for absorbing and collecting carbon dioxide from a gas containing carbon dioxide. The aqueous solution is characterized by containing at least one tertiary amine compound represented by general formula (1) [wherein n is a number selected from 1 and 2; R1 represents an alkyl group or a hydroxyalkyl group; and R2 is in position-2 or -3 and represents a hydrogen, an alkyl group or a hydroxyalkyl group; provided that at least one of R1 and R2 represents a hydroxyalkyl group].
Description
本発明は、ガス中に含まれる二酸化炭素（CO2）を、二酸化炭素吸収及び回収用水溶液を用いて吸収し、続いて二酸化炭素が吸収された二酸化炭素吸収及び回収用水溶液から二酸化炭素を脱離して回収する水溶液及び方法に関する。
The present invention absorbs carbon dioxide (CO 2 ) contained in a gas using an aqueous solution for carbon dioxide absorption and recovery, and subsequently desorbs carbon dioxide from the carbon dioxide absorption and recovery aqueous solution in which carbon dioxide is absorbed. The present invention relates to an aqueous solution and a method for recovering separately.
近年、地球温暖化に起因すると考えられる気象変動や災害の頻発が、農業生産、住環境、エネルギー消費等に多大の影響をおよぼしている。この地球温暖化は、人間の活動が活発になることに付随して増大する二酸化炭素、メタン、亜酸化窒素、フロン等の温室効果ガスが大気中に増大するためであると考えられている。その温室効果ガスの中で最も主要なものとして、大気中の二酸化炭素があげられる。地球温暖化の防止のため1997年12月には温暖化防止京都会議(COP3)が開催され、その会議で採択された京都議定書が2005年2月16日に発効し、二酸化炭素放出量の削減に向けての対策が緊急に必要となっている。
In recent years, meteorological fluctuations and frequent occurrence of disasters, which are thought to be caused by global warming, have had a great influence on agricultural production, living environment, energy consumption, and the like. This global warming is considered to be due to an increase in the atmosphere of greenhouse gases such as carbon dioxide, methane, nitrous oxide, and chlorofluorocarbon, which increase with the increase of human activities. The most important greenhouse gas is carbon dioxide in the atmosphere. To prevent global warming, the Kyoto Conference on Global Warming Prevention (COP3) was held in December 1997, and the Kyoto Protocol adopted at that conference entered into force on February 16, 2005, reducing CO2 emissions. There is an urgent need to take measures toward this.
二酸化炭素の発生源としては石炭、重油、天然ガス等を燃料とする火力発電所、製造所のボイラーあるいはセメント工場のキルン、コークスで酸化鉄を還元する製鐵所の高炉、そしてガソリン、重油、軽油等を燃料とする自動車、船舶、航空機等の輸送機器などがある。これらのうち輸送機器を除くものについては固定的な設備であり、二酸化炭素の放出を削減する対策を施しやすい設備として期待されている。
Sources of carbon dioxide include coal, heavy oil, natural gas and other thermal power plants, factory boilers or kilns in cement plants, blast furnace blast furnaces that reduce iron oxide with coke, gasoline, heavy oil, There are transportation equipment such as automobiles, ships, and aircraft that use light oil as fuel. Of these, those other than transportation equipment are fixed facilities, and are expected to be easy to implement measures to reduce carbon dioxide emissions.
ガス中の二酸化炭素を回収する方法としてはこれまでもいくつかの方法が知られている。そしてまた現在も広く種々の方法が研究されている。
There have been known several methods for recovering carbon dioxide in gas. And now, various methods are widely studied.
例えば、二酸化炭素を含むガスを吸収塔内でアルカノールアミン水溶液と接触させて二酸化炭素を吸収させた後、その二酸化炭素回収用水溶液を加熱して脱離塔で二酸化炭素を脱離回収させる方法は、1930年代から開発され、尿素合成プラント塔で実用化されている。この方法は、経済的でありかつ大型化しやすいものである。
For example, after a gas containing carbon dioxide is brought into contact with an alkanolamine aqueous solution in an absorption tower to absorb carbon dioxide, the carbon dioxide recovery aqueous solution is heated to desorb and recover carbon dioxide in the desorption tower. Developed since the 1930s and put into practical use in urea synthesis plant towers. This method is economical and easy to enlarge.
ここでアルカノールアミンとしては、モノエタノールアミン（以下、ＭＥＡと示すこともある）、ジエタノールアミン（以下、ＤＥＡと示すこともある）、トリエタノールアミン（以下、ＴＥＡと示すこともある）、メチルジエタノールアミン（以下、ＭＤＥＡと示すこともある）、ジイソプロパノールアミン（ＤＩＰＡ）、ジグリコールアミン（ＤＧＡ）等が知られているが、通常ＭＥＡが用いられている。
Here, examples of the alkanolamine include monoethanolamine (hereinafter sometimes referred to as MEA), diethanolamine (hereinafter sometimes referred to as DEA), triethanolamine (hereinafter sometimes referred to as TEA), methyldiethanolamine ( Hereinafter, it may be indicated as MDEA), diisopropanolamine (DIPA), diglycolamine (DGA), etc., but MEA is usually used.
しかし、これらのアルカノールアミンの水溶液を吸収液として用いた場合、装置材質の腐食性が高いため、装置に高価な耐食鋼を用いる必要があったり、吸収液中のアミン濃度を下げる必要がある。また、吸収した二酸化炭素が脱離しにくいために、脱離の温度を１２０℃と高い温度に加熱して脱離、回収する必要があった。また、それとは別に二酸化炭素を吸収液から脱離するのに必要なエネルギーが、85 kJ／molCO2と高いという欠点もある。例えば、この方法を用いて発電所において二酸化炭素を回収するには、発電量の２０％にもあたる余分なエネルギーが必要となってしまう。二酸化炭素の発生の削減、省エネルギー及び省資源が求められる時代においては、この高エネルギー消費は二酸化炭素吸収、回収設備の実用化を阻む大きな要因となっている。
However, when an aqueous solution of these alkanolamines is used as the absorbing solution, the corrosiveness of the device material is high, and therefore it is necessary to use expensive corrosion-resistant steel for the device or to reduce the amine concentration in the absorbing solution. Further, since the absorbed carbon dioxide is difficult to desorb, it was necessary to desorb and recover by heating the desorption temperature to a high temperature of 120 ° C. In addition, the energy required for desorbing carbon dioxide from the absorbing solution is also high at 85 kJ / mol CO 2 . For example, in order to collect carbon dioxide at a power plant using this method, extra energy equivalent to 20% of the power generation amount is required. In an era where reduction of carbon dioxide generation, energy saving and resource saving are required, this high energy consumption is a major factor that impedes the practical use of carbon dioxide absorption and recovery equipment.
例えば、特許文献１には、アミノ基周辺にアルキル基等の立体障害があるいわゆるヒンダードアミンの水溶液と大気圧下の燃焼排ガスとを接触させ、当該水溶液に二酸化炭素を吸収させることによる、燃料排ガス中の二酸化炭素の除去方法が記載されている。
For example, in Patent Document 1, a so-called hindered amine aqueous solution having a steric hindrance such as an alkyl group around an amino group is brought into contact with combustion exhaust gas under atmospheric pressure, and carbon dioxide is absorbed in the aqueous solution. A method for removing carbon dioxide is described.
当該特許文献１には、ヒンダードアミンとして２－メチルアミノエタノール（以下、ＭＡＥと示すこともある）及び２－エチルアミノエタノール（以下、ＥＡＥと示すこともある）の実施例が記され、ＭＡＥ及びＥＡＥの水溶液が、二酸化炭素の吸収に好ましいと記載されている。
In Patent Document 1, examples of 2-methylaminoethanol (hereinafter sometimes referred to as MAE) and 2-ethylaminoethanol (hereinafter sometimes referred to as EAE) as hindered amines are described, and MAE and EAE are described. Is described as being preferred for carbon dioxide absorption.
特許文献２には、アミン水溶液と混合ガスとを接触させて二酸化炭素を吸収する工程及び当該水溶液から二酸化炭素を脱離する工程を含む二酸化炭素の回収方法が記載されている。
Patent Document 2 describes a carbon dioxide recovery method including a step of bringing an aqueous amine solution and a mixed gas into contact with each other to absorb carbon dioxide and a step of desorbing carbon dioxide from the aqueous solution.
特許文献２には、アミン水溶液として、２級もしくは３級炭素と結合した２級アミノ基又は３級炭素と結合した１級アミノ基を含む化合物、例えば、２－メチルピペラジン（以下、２ＭＰＺと示すこともある）、２－アミノ－２－メチル－１－プロパノール（以下、ＡＭＰと示すこともある）等が記載されている。
Patent Document 2 discloses, as an aqueous amine solution, a compound containing a secondary amino group bonded to a secondary or tertiary carbon or a primary amino group bonded to a tertiary carbon, such as 2-methylpiperazine (hereinafter referred to as 2MPZ). 2) -amino-2-methyl-1-propanol (hereinafter sometimes referred to as AMP) and the like.
特許文献３には、吸収液の成分として分子内に1級、2級、3級の窒素を2つ以上又は全て有するアミン化合物の混合物が例示されており、1-(2-アミノエチル)ピペラジン、(1-メチル)(2-アミノ)-(5メチルアミノ)ピロリジン等が例示されている。
Patent Document 3 exemplifies a mixture of amine compounds having two or more primary, secondary, and tertiary nitrogens in the molecule as components of the absorbing solution. 1- (2-Aminoethyl) piperazine And (1-methyl) (2-amino)-(5methylamino) pyrrolidine and the like.
特許文献4には、吸収液を構成するアミン成分として水酸基またはヒドロキシアルキル基で置換された2級の環状アミン類が提案されているが、この場合の置換位置はいずれも炭素原子であり、アミノ基への直接置換化合物は含まれていない。
Patent Document 4 proposes secondary cyclic amines substituted with a hydroxyl group or a hydroxyalkyl group as an amine component constituting the absorbing solution. In this case, the substitution position is a carbon atom, Direct substitution compounds on the group are not included.
二酸化炭素の回収方法は、排ガス中からの二酸化炭素の除去、すなわち水溶液への二酸化炭素の吸収工程、及び二酸化炭素を吸収した水溶液からの二酸化炭素の脱離工程も高効率に行われ、その間の二酸化炭素回収に消費される回収エネルギーが低い事が要求されており、これを達成させる吸収液の開発が重要である。
In the method of recovering carbon dioxide, the removal of carbon dioxide from the exhaust gas, that is, the absorption process of carbon dioxide into the aqueous solution and the desorption process of carbon dioxide from the aqueous solution that absorbed carbon dioxide are performed with high efficiency. The recovery energy consumed for carbon dioxide recovery is required to be low, and it is important to develop an absorbing solution that can achieve this.
これまでの吸収液でのCO2回収エネルギーのレベルは経済性視点からみてまだ不充分であり大きな課題になっていると言わざるを得ない。特に回収エネルギーの大きな部分を占める二酸化炭素とアミン成分との反応に関する反応熱は、低減が難しくその開発には多くの努力がなされてきた。
特許第2871334号公報
米国特許4,112,052号明細書
特開2006-150298号公報
米国特許6,436,174号明細書
It must be said that the level of CO 2 recovery energy in the absorbent so far is still insufficient from an economic point of view and is a major issue. In particular, it has been difficult to reduce the heat of reaction related to the reaction between carbon dioxide, which accounts for a large portion of the recovered energy, and the amine component, and many efforts have been made to develop it.
Japanese Patent No. 2871334 U.S. Pat.No. 4,112,052 JP 2006-150298 A U.S. Patent 6,436,174
前述の様に各種の二酸化炭素を含むガスから二酸化炭素を効率よく回収する吸収液の開発が望まれており、特に二酸化炭素を吸収、脱離して回収する際の必要なエネルギーが少ない吸収液の開発が大きな課題である。
As described above, it is desired to develop an absorption liquid that efficiently recovers carbon dioxide from various carbon dioxide-containing gases. In particular, an absorption liquid that requires less energy when absorbing and desorbing and recovering carbon dioxide is required. Development is a major challenge.
吸収液を構成するアミン化合物に求められる基本性能である反応熱、反応速度、吸収量、脱離等の性能はそれぞれの性能間にトレードオフの関係がある事が知られており、すべてを満たす化合物の発見は難しく、実用上は特定の性能に優れる化合物を複数種組み合わせて吸収液の総合性能を調整する処方が取られてきている。例えば反応熱の低いアミン化合物が見出されればそれを吸収液の構成成分として用いる事により全体の回収エネルギーの低減に繋がる事となる。しかし、一般的には反応熱が低いアミン化合物は吸収速度が低くなる性能上のトレードオフの関係があり結果として、吸収液の吸収速度が低下しこれに対応する為、設備費の上昇を招く等の課題が発生する。従って、それらを回避できる新規なアミン化合物の開発が重要となってくるのである。
It is known that there are trade-offs between performances such as reaction heat, reaction rate, absorption amount, desorption, etc., which are the basic performances required for amine compounds that make up the absorbing solution, satisfying all of them. It is difficult to find a compound, and in practice, a prescription for adjusting the overall performance of the absorbent by combining a plurality of compounds having excellent specific performance has been taken. For example, if an amine compound having a low reaction heat is found, using it as a constituent component of the absorbing liquid leads to a reduction in the overall recovered energy. However, in general, amine compounds with low reaction heat have a trade-off relationship in performance that lowers the absorption rate. As a result, the absorption rate of the absorption liquid decreases and this increases the equipment cost. Such problems occur. Therefore, the development of new amine compounds that can avoid them becomes important.
以上の従来技術の問題点に鑑み、本発明は、ガス中二酸化炭素の吸収及び回収を高効率に行う為、低いエネルギー消費量で、高純度の二酸化炭素を回収する水溶液及び方法を提供することを目的とする。具体的には、二酸化炭素とアミンとの反応熱が低い第3級アミン化合物を少なくとも1種含む水溶液、並びに当該水溶液を使用することにより二酸化炭素吸収及び回収に要する全体のエネルギーを低下させ高純度の二酸化炭素を低コストで回収する方法を提供することを目的とするものである。
In view of the above problems of the prior art, the present invention provides an aqueous solution and method for recovering high purity carbon dioxide with low energy consumption in order to efficiently absorb and recover carbon dioxide in gas. With the goal. Specifically, an aqueous solution containing at least one tertiary amine compound that has a low heat of reaction between carbon dioxide and an amine, and the use of the aqueous solution reduces the overall energy required for carbon dioxide absorption and recovery, resulting in high purity. It aims at providing the method of collect | recovering the carbon dioxide of this at low cost.
本発明者らは、上記課題を解決するために、鋭意研究した結果、一般式〔１〕で表される第3級アミン化合物の二酸化炭素との反応熱が従来の第3級アミンより低いことを見出した。前述のように吸収に用いるアミンの性能を特徴付ける反応熱、反応速度、吸収量、及び脱離の各性能はトレードオフの関係があり、一般的には反応熱が低いアミンは吸収速度、吸収量が低下する欠点を持つが、本発明による第3級アミンは、驚くべきことにこれらの性能低下が小さく従来にはない特性を持つものであり、従来のトレードオフの関係に縛られない優れた性能を持つことがわかった。この二酸化炭素とアミン化合物の反応熱の低下は、結果として二酸化炭素の脱離時に加える熱エネルギーの低減に繋がり二酸化炭素回収における全体の回収エネルギーの低減を可能とし本発明の課題を解決するものである。
As a result of intensive studies to solve the above problems, the present inventors have found that the heat of reaction of the tertiary amine compound represented by the general formula [1] with carbon dioxide is lower than that of the conventional tertiary amine. I found. As described above, the reaction heat, reaction rate, absorption amount, and desorption performance that characterize the performance of amines used for absorption are in a trade-off relationship. Generally, amines with low reaction heat have absorption rates and absorption amounts. However, the tertiary amine according to the present invention is surprisingly small in performance degradation and has unprecedented characteristics, and is excellent without being bound by the conventional trade-off relationship. It turns out that it has performance. This reduction in the heat of reaction between carbon dioxide and the amine compound results in a reduction in the thermal energy applied during the desorption of carbon dioxide, enabling a reduction in the overall recovery energy in carbon dioxide recovery and solving the problems of the present invention. is there.
本発明のアミンを水溶液の一部として含む水溶液は、二酸化炭素を工業的、経済的に回収するのに要請される吸収速度、脱離速度を持ち、なおかつ全体の回収エネルギーが従来より小さい優れた性能を持つことを見出した。かかる知見に基づき、更に研究を重ねた結果、本発明を完成するに至った。
The aqueous solution containing the amine of the present invention as a part of the aqueous solution has an absorption rate and a desorption rate required for industrially and economically recovering carbon dioxide, and the overall recovery energy is smaller than before. It has been found that it has performance. As a result of further research based on this knowledge, the present invention has been completed.
即ち、本発明は以下の項1から項6の構成をなすものである。
項１．二酸化炭素を含むガスから二酸化炭素を吸収及び回収するための水溶液であって、一般式〔1〕で表される第3級アミン化合物を少なくとも1種含むことを特徴とする水溶液。
一般式〔1〕： That is, the present invention constitutes the following items 1 to 6.
Item 1. An aqueous solution for absorbing and recovering carbon dioxide from a gas containing carbon dioxide, wherein the aqueous solution contains at least one tertiary amine compound represented by the general formula [1].
General formula [1]:
項１．二酸化炭素を含むガスから二酸化炭素を吸収及び回収するための水溶液であって、一般式〔1〕で表される第3級アミン化合物を少なくとも1種含むことを特徴とする水溶液。
一般式〔1〕： That is, the present invention constitutes the following items 1 to 6.
Item 1. An aqueous solution for absorbing and recovering carbon dioxide from a gas containing carbon dioxide, wherein the aqueous solution contains at least one tertiary amine compound represented by the general formula [1].
General formula [1]:
（式中、nは1又は2から選ばれ、R1はアルキル基又はヒドロキシアルキル基を表し、R2は2位又は3位であり、R2は水素、アルキル基又はヒドロキシアルキル基を表し、R1及びR2の少なくとも一方がヒドロキシアルキル基を表す。）
項２．一般式〔1〕の第3級アミン化合物が1-メチル-2-ピペリジンメタノール、1-メチル-2-ピペリジンエタノール、1-メチル-3-ピペリジンメタノール、1-エチル-2-ピペリジンメタノール、1-エチル-3-ピペリジンメタノール、1-エチル-2-ピペリジンエタノール、1-(2-ヒドロキシエチル)ピロリジン、1-(2-ヒドロキシエチル)ピペリジン及び1-(3-ヒロキシプロピル)ピロリジンからなる群より選ばれる少なくとも1種である１に記載の水溶液。
項３．一般式〔1〕の第3級アミン化合物の含有量が5～45重量%である項１又は２に記載の水溶液。
項４．更に、アルカノールアミン類、及びピペラジン類からなる群より選ばれる少なくとも1種を含む項１～３のいずれかに記載の水溶液。
項５．アルカノールアミン類が、2-(イソプロピルアミノ)エタノール、2-(エチルアミノ)エタノール及び2-アミノ-2-メチル-1-プロパノールからなる群より選ばれる少なくとも1種である項４に記載の水溶液。
項６．ピペラジン類が、ピペラジン、2-メチルピペラジン及び2,6-ジメチルピペラジンからなる群より選ばれる少なくとも1種である項４又は５に記載の水溶液。
項７．（１）項１～６のいずれかに記載の水溶液に接触させて該水溶液に二酸化炭素を吸収させる工程、及び
（２）上記（１）で得られた二酸化炭素が吸収された水溶液を加熱して、二酸化炭素を脱離して回収する工程、
を含む二酸化炭素の吸収及び回収方法。 (In the formula, n is selected from 1 or 2, R 1 represents an alkyl group or a hydroxyalkyl group, R 2 is a 2-position or a 3-position, R 2 represents hydrogen, an alkyl group or a hydroxyalkyl group, At least one of R 1 and R 2 represents a hydroxyalkyl group.)
Item 2. The tertiary amine compound of the general formula [1] is 1-methyl-2-piperidinemethanol, 1-methyl-2-piperidineethanol, 1-methyl-3-piperidinemethanol, 1-ethyl-2-piperidinemethanol, 1- From the group consisting of ethyl-3-piperidinemethanol, 1-ethyl-2-piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) piperidine and 1- (3-hydroxypropyl) pyrrolidine 2. The aqueous solution according to 1, which is at least one selected.
Item 3. Item 3. The aqueous solution according to Item 1 or 2, wherein the content of the tertiary amine compound of the general formula [1] is 5 to 45% by weight.
Item 4. Item 4. The aqueous solution according to any one of Items 1 to 3, further comprising at least one selected from the group consisting of alkanolamines and piperazines.
Item 5. Item 5. The aqueous solution according to Item 4, wherein the alkanolamine is at least one selected from the group consisting of 2- (isopropylamino) ethanol, 2- (ethylamino) ethanol, and 2-amino-2-methyl-1-propanol.
Item 6. Item 6. The aqueous solution according to Item 4 or 5, wherein the piperazine is at least one selected from the group consisting of piperazine, 2-methylpiperazine and 2,6-dimethylpiperazine.
Item 7. (1) A step of bringing the aqueous solution into contact with the aqueous solution according to any one of Items 1 to 6 to absorb carbon dioxide, and (2) heating the aqueous solution having absorbed carbon dioxide obtained in (1) above. Desorbing and recovering carbon dioxide,
Carbon dioxide absorption and recovery method comprising:
項２．一般式〔1〕の第3級アミン化合物が1-メチル-2-ピペリジンメタノール、1-メチル-2-ピペリジンエタノール、1-メチル-3-ピペリジンメタノール、1-エチル-2-ピペリジンメタノール、1-エチル-3-ピペリジンメタノール、1-エチル-2-ピペリジンエタノール、1-(2-ヒドロキシエチル)ピロリジン、1-(2-ヒドロキシエチル)ピペリジン及び1-(3-ヒロキシプロピル)ピロリジンからなる群より選ばれる少なくとも1種である１に記載の水溶液。
項３．一般式〔1〕の第3級アミン化合物の含有量が5～45重量%である項１又は２に記載の水溶液。
項４．更に、アルカノールアミン類、及びピペラジン類からなる群より選ばれる少なくとも1種を含む項１～３のいずれかに記載の水溶液。
項５．アルカノールアミン類が、2-(イソプロピルアミノ)エタノール、2-(エチルアミノ)エタノール及び2-アミノ-2-メチル-1-プロパノールからなる群より選ばれる少なくとも1種である項４に記載の水溶液。
項６．ピペラジン類が、ピペラジン、2-メチルピペラジン及び2,6-ジメチルピペラジンからなる群より選ばれる少なくとも1種である項４又は５に記載の水溶液。
項７．（１）項１～６のいずれかに記載の水溶液に接触させて該水溶液に二酸化炭素を吸収させる工程、及び
（２）上記（１）で得られた二酸化炭素が吸収された水溶液を加熱して、二酸化炭素を脱離して回収する工程、
を含む二酸化炭素の吸収及び回収方法。 (In the formula, n is selected from 1 or 2, R 1 represents an alkyl group or a hydroxyalkyl group, R 2 is a 2-position or a 3-position, R 2 represents hydrogen, an alkyl group or a hydroxyalkyl group, At least one of R 1 and R 2 represents a hydroxyalkyl group.)
Item 2. The tertiary amine compound of the general formula [1] is 1-methyl-2-piperidinemethanol, 1-methyl-2-piperidineethanol, 1-methyl-3-piperidinemethanol, 1-ethyl-2-piperidinemethanol, 1- From the group consisting of ethyl-3-piperidinemethanol, 1-ethyl-2-piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) piperidine and 1- (3-hydroxypropyl) pyrrolidine 2. The aqueous solution according to 1, which is at least one selected.
Item 3. Item 3. The aqueous solution according to Item 1 or 2, wherein the content of the tertiary amine compound of the general formula [1] is 5 to 45% by weight.
Item 4. Item 4. The aqueous solution according to any one of Items 1 to 3, further comprising at least one selected from the group consisting of alkanolamines and piperazines.
Item 5. Item 5. The aqueous solution according to Item 4, wherein the alkanolamine is at least one selected from the group consisting of 2- (isopropylamino) ethanol, 2- (ethylamino) ethanol, and 2-amino-2-methyl-1-propanol.
Item 6. Item 6. The aqueous solution according to Item 4 or 5, wherein the piperazine is at least one selected from the group consisting of piperazine, 2-methylpiperazine and 2,6-dimethylpiperazine.
Item 7. (1) A step of bringing the aqueous solution into contact with the aqueous solution according to any one of Items 1 to 6 to absorb carbon dioxide, and (2) heating the aqueous solution having absorbed carbon dioxide obtained in (1) above. Desorbing and recovering carbon dioxide,
Carbon dioxide absorption and recovery method comprising:
本発明の二酸化炭素の吸収液を用いた二酸化炭素の分離回収方法は、公知の二酸化炭素の吸収用水溶液に比較して、低いエネルギー消費量でガス中の二酸化炭素を吸収および脱離して高純度の二酸化炭素を回収することができる。又、第3級アミンの使用により付随するとされてきた吸収速度の低下が小さく、これにより二酸化炭素を回収する際の全体の回収熱を低減させ、設備効率も改良することが出来る。結果としては二酸化炭素単位重量当たりの回収エネルギーの低減が可能となり現在課題となっている回収コストの削減に繋がるものである。又、この事は、二酸化炭素を回収、脱離する為の吸収塔、脱離塔及びこれらに付随する装置を小型化し、エネルギー損失を削減し、合わせて建設費用を減らすことが可能となる。
The method for separating and recovering carbon dioxide using the carbon dioxide absorbing liquid of the present invention has a high purity by absorbing and desorbing carbon dioxide in the gas with a lower energy consumption compared to known aqueous solutions for absorbing carbon dioxide. Of carbon dioxide can be recovered. In addition, the decrease in absorption rate, which has been accompanied by the use of a tertiary amine, is small, thereby reducing the overall recovery heat when recovering carbon dioxide and improving the equipment efficiency. As a result, it is possible to reduce the recovered energy per unit weight of carbon dioxide, which leads to the reduction of the recovery cost that is currently an issue. This also makes it possible to reduce the size of the absorption tower, the desorption tower, and the devices associated therewith for recovering and desorbing carbon dioxide, thereby reducing energy loss and reducing the construction cost.
以下、本発明を詳述する。
Hereinafter, the present invention will be described in detail.
二酸化炭素吸収及び回収用水溶液
本発明の水溶液は、一般式〔1〕で表される第3級アミン化合物を少なくとも1種含むことを特徴とする。
一般式〔1〕： Aqueous solution for absorbing and recovering carbon dioxide The aqueous solution of the present invention is characterized by containing at least one tertiary amine compound represented by the general formula [1].
General formula [1]:
本発明の水溶液は、一般式〔1〕で表される第3級アミン化合物を少なくとも1種含むことを特徴とする。
一般式〔1〕： Aqueous solution for absorbing and recovering carbon dioxide The aqueous solution of the present invention is characterized by containing at least one tertiary amine compound represented by the general formula [1].
General formula [1]:
式中、nは1又は2から選ばれる。又、一般式〔1〕のR1としてはアルキル基又はヒドロキシアルキル基が挙げられ、R1がアルキル基の場合は炭素数が１～３のものが好ましく、ヒドロキシアルキル基の場合は炭素数が２又は３のものが好ましい。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ヒドロキシエチル基、ヒドロキシプロピル基等が挙げられるが、好ましくはメチル基、エチル基、ヒドロキシエチル基及びヒドロキシプロピル基が選ばれる。
In the formula, n is selected from 1 or 2. Further, R 1 in the general formula [1] includes an alkyl group or a hydroxyalkyl group. When R 1 is an alkyl group, it preferably has 1 to 3 carbon atoms, and when it is a hydroxyalkyl group, it has a carbon number. Two or three are preferred. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hydroxyethyl group, a hydroxypropyl group, and the like, and a methyl group, an ethyl group, a hydroxyethyl group, and a hydroxypropyl group are preferably selected.
又、一般式〔１〕のR2としては水素、アルキル基又はヒドロキシアルキル基が挙げられ、アルキル基及びヒドロキシアルキル基の炭素数は好ましくは１～３である。具体的には、水素、メチル基、エチル基、プロピル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基等が挙げられるが、好ましくは水素、メチル基、エチル基、ヒドロキシメチル基、ヒドロキシエチル基及びヒドロキシプロピル基が選ばれる。
In addition, R 2 in the general formula [1] includes hydrogen, an alkyl group, or a hydroxyalkyl group, and the alkyl group and the hydroxyalkyl group preferably have 1 to 3 carbon atoms. Specific examples include hydrogen, methyl group, ethyl group, propyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc., preferably hydrogen, methyl group, ethyl group, hydroxymethyl group, hydroxyethyl group And a hydroxypropyl group are selected.
一般式〔１〕のR1及びR2の少なくとも一方は、ヒドロキシアルキル基である。
At least one of R 1 and R 2 in the general formula [1] is a hydroxyalkyl group.
さらに、R1とR2の組み合わせについては、R1がヒドロキシアルキル基(好ましくは炭素数２又は３)の場合はR2は水素又はアルキル基(好ましくは炭素数１～３)が好ましく、R1がアルキル基(好ましくは炭素数１～３)の場合はR2はヒドロキシアルキル基(好ましくは炭素数１～３)を選択する組み合わせが好ましい。R2の置換位置については2,3位置換が選択される。
Further, regarding the combination of R 1 and R 2 , when R 1 is a hydroxyalkyl group (preferably having 2 or 3 carbon atoms), R 2 is preferably hydrogen or an alkyl group (preferably having 1 to 3 carbon atoms) When 1 is an alkyl group (preferably having 1 to 3 carbon atoms), R 2 is preferably a combination of selecting a hydroxyalkyl group (preferably having 1 to 3 carbon atoms). For the substitution position of R 2 , substitution at the 2- and 3-position is selected.
具体的には、R1がアルキル基の場合、１-メチル-2-ピペリジンメタノール(以下、M2PPMと示すこともある)、１-メチル-2-ピペリジンエタノール(以下、M2PPEと示すこともある)、1-メチル-3-ピペリジンメタノール、1-エチル-2-ピペリジンメタノール(以下、E2PPMと示すこともある)、1-メチル-3-ピペリジンメタノール、1-エチル-3-ピペリジンメタノール(E3PPM)、 1-エチル-2-ピペリジンエタノール等が選ばれる。又、R2が水素の場合、1-(2ヒドロキシエチル)-ピロリジン(以下、HEPLと示すこともある)、1-(2ヒドロキシエチル)-ピペリジン(以下、HEPPと示すこともある)、1-(3-ヒロキシプロピル)ピロリジン等が選ばれる。
Specifically, when R 1 is an alkyl group, 1-methyl-2-piperidinemethanol (hereinafter also referred to as M2PPM), 1-methyl-2-piperidineethanol (hereinafter also referred to as M2PPE) 1-methyl-3-piperidinemethanol, 1-ethyl-2-piperidinemethanol (hereinafter sometimes referred to as E2PPM), 1-methyl-3-piperidinemethanol, 1-ethyl-3-piperidinemethanol (E3PPM), 1-ethyl-2-piperidineethanol or the like is selected. When R 2 is hydrogen, 1- (2 hydroxyethyl) -pyrrolidine (hereinafter also referred to as HEPL), 1- (2 hydroxyethyl) -piperidine (hereinafter also referred to as HEPP), 1 -(3-Hydroxypropyl) pyrrolidine and the like are selected.
本出願での第3級アミン化合物は、公知のものが大半であり、試薬でも入手可能であるが、代表的な化合物に付き以下に製造方法を記す。
Most of the tertiary amine compounds in the present application are known and can be obtained as reagents, but the production methods are described below for typical compounds.
本願の一般式〔1〕で表される第3級アミン化合物のうちR2が水素で、R1がヒドロキシアルキル基の場合は、対応する2級アミンと対応するハロゲン化アルコールとの縮合反応例(O.S,Coll.Vol.2,p183(1943))と類似の反応をした後、アルカリ処理をして抽出、蒸留等の手法により得られる。
In the tertiary amine compound represented by the general formula [1] of the present application, when R 2 is hydrogen and R 1 is a hydroxyalkyl group, a condensation reaction example of the corresponding secondary amine and the corresponding halogenated alcohol (OS, Coll. Vol. 2, p183 (1943)). After the reaction, it is obtained by an alkali treatment, extraction, distillation or the like.
R1がアルキル基でR2がヒドロキシアルキル基の場合、例えば1-メチル-ピペリジンメタノールの場合は、公知の2-ピペリジンメタノールをメタノールでメチル化する事により得ることが出来る(European Journal of Inorganic Chemistry, (3),524-529;2004)。
When R 1 is an alkyl group and R 2 is a hydroxyalkyl group, for example, 1-methyl-piperidinemethanol, it can be obtained by methylating a known 2-piperidinemethanol with methanol (European Journal of Inorganic Chemistry (3), 524-529; 2004).
本発明による化合物〔1〕が反応熱が低く結果として全体の回収エネルギー低減に効果を示す理由は、環状アミン誘導体が二酸化炭素を吸収する反応時の立体的効果によるものと推定している。
The reason why the compound [1] according to the present invention has a low heat of reaction and as a result has an effect on reducing the overall recovered energy is presumed to be due to a steric effect during the reaction in which the cyclic amine derivative absorbs carbon dioxide.
本発明では二酸化炭素を吸収する反応は発熱反応であり、逆の二酸化炭素を脱離する反応は吸熱反応である。本発明において、反応熱は二酸化炭素を吸収する際に発生する熱又は二酸化炭素を脱離する際に外部より吸収する熱の意味として用いる。
In the present invention, the reaction that absorbs carbon dioxide is an exothermic reaction, and the reaction that desorbs the opposite carbon dioxide is an endothermic reaction. In the present invention, reaction heat is used as meaning heat generated when absorbing carbon dioxide or heat absorbed from the outside when desorbing carbon dioxide.
一般的には、第1,2級アミンの様に窒素原子上に水素を持つアミンの場合は、二酸化炭素との反応では、アミンと二酸化炭素が結合したカーバメイトとプロトン化アミンとが生成する。一方、第3級アミンの場合は、窒素原子上に水素を持たない為、カーバメイトは出来ず、二酸化炭素との反応に於いては、二酸化炭素と水との反応で生成する重炭酸イオンと、プロトン化アミンとでバイカーボネートが生成することにより進行する事が知られている。カーバメイトと、バイカーボネートの結合におけるこの差が、1,2級アミンと3級アミンの発熱量の差となるのである。
In general, in the case of an amine having hydrogen on a nitrogen atom, such as primary and secondary amines, carbamate and protonated amine in which amine and carbon dioxide are combined are produced in the reaction with carbon dioxide. On the other hand, in the case of a tertiary amine, since there is no hydrogen on the nitrogen atom, carbamate is not possible, and in the reaction with carbon dioxide, bicarbonate ions generated by the reaction of carbon dioxide and water, It is known to proceed by forming a bicarbonate with a protonated amine. This difference in the bond between carbamate and bicarbonate is the difference in calorific value between 1,2 and 3 amines.
因みに、二酸化炭素の吸収によく使用される前述のMEAは代表的な第1級アミンであり二酸化炭素の反応熱は約85 kJ/モルCO2であるが、第3級アミンの代表例であるMDEAでは反応熱は約65 kJ/モルCO2と大幅に低い数値となる。
Incidentally, the aforementioned MEA, which is often used for carbon dioxide absorption, is a typical primary amine, and the reaction heat of carbon dioxide is about 85 kJ / mole CO 2 , but it is a typical example of a tertiary amine. In MDEA, the heat of reaction is about 65 kJ / mol CO 2, which is a very low value.
しかしながら、反応速度の相対比はMEAを1.0とすると、MDEAは、0.2と小さく反応熱の低減が反応速度の低下を招くというトレードオフの関係にあるのは前述のとおりである。
However, when the relative ratio of the reaction rates is set to 1.0, the MDEA is as small as 0.2, and as described above, there is a trade-off relationship that a reduction in reaction heat leads to a decrease in reaction rate.
本発明による環状アミン誘導体では、アミノ基が3級であるだけでなく、ヒドロキシアルキル基が分子内に導入されているので、二酸化炭素とアミンとの反応の結果生じるプロトン化アミンがヒドロキシアルキルの水酸基と水素結合を形成することにより安定化される。このため一般的な3級アミンより少ない発熱量で二酸化炭素の吸収が進むと推定される。この概念をM2PPMを例にとって以下の反応式に示すが、反応生成物である重炭酸塩が本発明化合物においてはその立体的特性により安定化構造をとり反応熱の低減に繋がることが推定される。
In the cyclic amine derivative according to the present invention, not only the amino group is tertiary, but also a hydroxyalkyl group is introduced into the molecule, so that the protonated amine resulting from the reaction between carbon dioxide and the amine is a hydroxyalkyl hydroxyl group. By forming a hydrogen bond with. For this reason, it is presumed that the absorption of carbon dioxide proceeds with a calorific value less than that of a general tertiary amine. This concept is shown in the following reaction formula taking M2PPM as an example, but it is estimated that the reaction product bicarbonate has a stabilized structure due to its steric properties in the compound of the present invention, leading to a reduction in reaction heat. .
又、驚くべきことに本発明による第3級アミンはその特性として反応熱が通常のアミンMDEAより低いだけでなく、低反応熱になると付随する速度低下が見られないという点で従来とは全く違う性能を示すものである。
Surprisingly, the tertiary amine according to the present invention has a characteristic that not only the heat of reaction is lower than that of the normal amine MDEA but also that the accompanying rate decrease is not observed at low heat of reaction. It shows different performance.
具体的には、MDEAの吸収速度(3 mol/L濃度)が0.8 g/L/minであるのに対して、本発明による1-メチル2-ピペリジンメタノールは同一濃度で2.7 g/L/minを示した。これも同様に本発明の化合物が反応進行の過程において示す立体的な効果の現れと考えられる。
Specifically, the absorption rate of MDEA (concentration of 3 μmol / L) is 0.8 μg / L / min, whereas 1-methyl 2-piperidinemethanol according to the present invention is 2.7 μg / L / min at the same concentration. showed that. This is also considered to be a manifestation of the steric effect that the compound of the present invention shows in the course of the reaction.
本発明に基づく水溶液の調製は、一般式〔1〕で表される第3級アミンにアルカノールアミン類、及びピペラジン類の群より選択される少なくとも1種を混合し水溶液全体の性能を調整してもよい。一般式〔1〕で表される第3級アミン化合物の使用により結果として水溶液としての反応熱の低減、反応速度の向上を達成することが可能となり、二酸化炭素の吸収及び回収に伴う全体のエネルギー消費も低減され経済的な効果が発揮されることとなる。
The aqueous solution based on the present invention is prepared by mixing the tertiary amine represented by the general formula [1] with at least one selected from the group of alkanolamines and piperazines to adjust the performance of the entire aqueous solution. Also good. As a result, the use of the tertiary amine compound represented by the general formula [1] can reduce the heat of reaction as an aqueous solution and improve the reaction rate, and the overall energy associated with the absorption and recovery of carbon dioxide. Consumption will be reduced and economic effects will be exerted.
一般式〔1〕で表される第3級アミン化合物以外の水溶液を構成する成分としてアルカノールアミン類とピペラジン類が挙げられるが、アルカノールアミン類としては、第1,2,3級のアミンが選択し得るが、好ましくは2-(イソプロピルアミノ)エタノール(以下、IPAEと示すこともある)、及び2-(エチルアミノ)エタノール、2-アミノ-2-メチル-1-プロパノールが選ばれる。
Alkanolamines and piperazines are listed as constituents of the aqueous solution other than the tertiary amine compound represented by the general formula [1]. As the alkanolamines, primary, secondary and tertiary amines are selected. However, 2- (isopropylamino) ethanol (hereinafter sometimes referred to as IPAE), 2- (ethylamino) ethanol, and 2-amino-2-methyl-1-propanol are preferably selected.
又、ピペラジン類としては、ピペラジン単体、及びピペラジンの環状部にアルキル置換を持つものが挙げられるが、好ましくはピペラジン(以下、PZと示すこともある)、2-メチルピペラジン、及び2,6-ジメチルピペラジンが選ばれる。これらは二酸化炭素の吸収時の反応活性剤として機能する。
Piperazines include piperazine alone and those having an alkyl substitution in the cyclic part of piperazine, preferably piperazine (hereinafter sometimes referred to as PZ), 2-methylpiperazine, and 2,6- Dimethyl piperazine is selected. These function as a reaction activator upon absorption of carbon dioxide.
本発明の水溶液中の一般式〔1〕で表される第3級アミンの含有量は、通常5～45重量%、好ましくは8～40重量%、より好ましくは10～35重量%である。
The content of the tertiary amine represented by the general formula [1] in the aqueous solution of the present invention is usually 5 to 45% by weight, preferably 8 to 40% by weight, more preferably 10 to 35% by weight.
又、本発明の水溶液中のアルカノールアミン類の含有量は、通常は5～50重量%、好ましくは10～45重量%、より好ましくは15～40重量%である。
Further, the content of alkanolamines in the aqueous solution of the present invention is usually 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 15 to 40% by weight.
さらに、本発明の水溶液中のピペラジン類の含有量は、通常は1～15重量%、好ましくは2～10重量%、より好ましくは3～9重量%である。
Furthermore, the content of piperazine in the aqueous solution of the present invention is usually 1 to 15% by weight, preferably 2 to 10% by weight, more preferably 3 to 9% by weight.
本発明の水溶液の各アミン成分の比率は、各々のアミンの反応熱、吸収量、吸収速度、及び脱離性能を考慮して最適な組成が選ばれる。本発明による第3級アミンの組成比率を上げる事が水溶液全体の反応熱を低下させる効果はあるが、実用的には吸収量、脱離量等も含めた性能設計が必要であり、これらの調整を実施し水溶液組成の比率を設定する。
As the ratio of each amine component in the aqueous solution of the present invention, an optimal composition is selected in consideration of the reaction heat, absorption amount, absorption rate, and desorption performance of each amine. Increasing the composition ratio of the tertiary amine according to the present invention has the effect of reducing the heat of reaction of the entire aqueous solution, but practically performance design including absorption amount, desorption amount, etc. is necessary. Make adjustments and set the ratio of aqueous solution composition.
本発明による水溶液の全アミン化合物の含量は20～65重量%が選択されるが、好ましくは30～60重量%の範囲が選ばれる。
The content of the total amine compound in the aqueous solution according to the present invention is selected to be 20 to 65% by weight, preferably 30 to 60% by weight.
一般的にはアミン成分の濃度が高い方が単位液容量あたりの二酸化炭素の吸収量、脱離量及び脱離速度が大きく、エネルギー消費やプラント設備の大きさや効率からは望ましいが、重量濃度として７０％を越える場合、活性剤としての水の効果が減少するためか二酸化炭素の吸収量が減少する。またアミン成分が水と均一に混合しない、粘度が上昇する、二酸化炭素を吸収して液のｐＨが低下した時泡立ちや乳化状態になる等の問題が生じることもある。
In general, the higher the concentration of the amine component, the greater the amount of carbon dioxide absorbed, the amount of desorption, and the rate of desorption per unit liquid volume, which is desirable in terms of energy consumption and the size and efficiency of plant equipment. If it exceeds 70%, the amount of carbon dioxide absorbed decreases because the effect of water as an activator decreases. Also, problems such as foaming or emulsification may occur when the amine component is not mixed with water uniformly, the viscosity increases, or when the pH of the liquid is lowered by absorbing carbon dioxide.
又、本発明で用いる水溶液には、必要に応じて腐食防止剤、酸化安定剤等を加えても良い。
Moreover, you may add a corrosion inhibitor, an oxidation stabilizer, etc. to the aqueous solution used by this invention as needed.
二酸化炭素吸収工程
本発明の二酸化炭素の吸収及び回収方法は、上記二酸化炭素吸収及び回収用水溶液に、二酸化炭素を含むガスを接触させて該水溶液に二酸化炭素を吸収させる工程を含む。 Carbon dioxide absorption step The carbon dioxide absorption and recovery method of the present invention includes a step of bringing a carbon dioxide-containing gas into contact with the carbon dioxide absorption and recovery aqueous solution to cause the aqueous solution to absorb carbon dioxide.
本発明の二酸化炭素の吸収及び回収方法は、上記二酸化炭素吸収及び回収用水溶液に、二酸化炭素を含むガスを接触させて該水溶液に二酸化炭素を吸収させる工程を含む。 Carbon dioxide absorption step The carbon dioxide absorption and recovery method of the present invention includes a step of bringing a carbon dioxide-containing gas into contact with the carbon dioxide absorption and recovery aqueous solution to cause the aqueous solution to absorb carbon dioxide.
二酸化炭素を含むガスとしては、例えば、重油、天然ガス等を燃料とする火力発電所、製造所のボイラーあるいはセメント工場のキルン、コークスで酸化鉄を還元する製鐵所の高炉、銑鉄中の炭素を燃焼して製鋼する同じく製鉄所の転炉等からの排ガスが挙げられ、該ガス中の二酸化炭素濃度は、通常5～30体積％程度、特に10～25体積%程度であればよい。かかる二酸化炭素濃度範囲では、本発明の作用効果が好適に発揮される。なお、二酸化炭素を含むガスには、二酸化炭素以外に水蒸気、CO、H2S、COS等のガスが含まれていてもよい。
Gases containing carbon dioxide include, for example, thermal power plants fueled with heavy oil, natural gas, etc., kilns at manufacturing plants or kilns at cement plants, blast furnaces at ironworks that reduce iron oxide with coke, carbon in pig iron Exhaust gas from a converter in the same ironworks where the steel is burned to produce steel, and the carbon dioxide concentration in the gas is usually about 5 to 30% by volume, particularly about 10 to 25% by volume. In such a carbon dioxide concentration range, the effects of the present invention are suitably exhibited. Note that the gas containing carbon dioxide may contain gas such as water vapor, CO, H 2 S, and COS in addition to carbon dioxide.
二酸化炭素を含むガスを、該水溶液に接触させる方法は特に限定はない。例えば、該水溶液中に二酸化炭素を含むガスをバブリングさせて吸収する方法、二酸化炭素を含むガス気流中に該水溶液を霧状に降らす方法（噴霧乃至スプレー方式）、あるいは磁製や金属網製の充填材の入った吸収塔内で二酸化炭素を含むガスと該水溶液を向流接触させる方法などによって行われる。
The method for bringing a gas containing carbon dioxide into contact with the aqueous solution is not particularly limited. For example, a method of bubbling and absorbing a gas containing carbon dioxide in the aqueous solution, a method of dropping the aqueous solution into a gas stream containing carbon dioxide (a spraying or spraying method), or a magnetic or metal mesh This is performed by a method in which a gas containing carbon dioxide and the aqueous solution are brought into countercurrent contact in an absorption tower containing a filler.
本発明の水溶液と二酸化炭素を含むガスを接触させ二酸化炭素を吸収させる時の温度は30～70℃の範囲が好ましい。二酸化炭素吸収時の圧力は通常ほぼ大気圧で行われる。吸収性能を高めるためより高い圧力まで加圧することもできるが、圧縮のために要するエネルギー消費を抑えるため大気圧下で行うのが好ましい。
The temperature when the aqueous solution of the present invention and a gas containing carbon dioxide are brought into contact with each other to absorb carbon dioxide is preferably in the range of 30 to 70 ° C. The pressure during carbon dioxide absorption is usually about atmospheric pressure. Although it is possible to pressurize to a higher pressure in order to enhance the absorption performance, it is preferable to carry out under atmospheric pressure in order to suppress energy consumption required for compression.
二酸化炭素の脱離工程
本発明の方法は、上記（１）の二酸化炭素吸収工程で得られた二酸化炭素が吸収された水溶液を加熱して、二酸化炭素を脱離して回収する工程を含む。 Carbon dioxide desorption step The method of the present invention includes a step of heating and recovering the carbon dioxide-absorbed aqueous solution obtained in the carbon dioxide absorption step of (1) above.
本発明の方法は、上記（１）の二酸化炭素吸収工程で得られた二酸化炭素が吸収された水溶液を加熱して、二酸化炭素を脱離して回収する工程を含む。 Carbon dioxide desorption step The method of the present invention includes a step of heating and recovering the carbon dioxide-absorbed aqueous solution obtained in the carbon dioxide absorption step of (1) above.
二酸化炭素を吸収した水溶液から二酸化炭素を脱離し、純粋なあるいは高濃度の二酸化炭素を回収する方法としては、蒸留と同じく水溶液を加熱して釜で泡立てて脱離する方法、棚段塔、スプレー塔及び磁製や金属網製の充填材の入った脱離塔内で液界面を広げて加熱する方法などが挙げられる。これにより、カーバメイトやバイカーボネートから二酸化炭素が遊離して放出される。
As a method of desorbing carbon dioxide from an aqueous solution that has absorbed carbon dioxide and recovering pure or high-concentration carbon dioxide, a method of heating the aqueous solution and removing it by bubbling in a kettle as in distillation, a plate tower, a spray Examples include a method in which a liquid interface is widened and heated in a tower and a desorption tower containing a magnetic or metal mesh filler. Thereby, carbon dioxide is liberated and released from carbamate and bicarbonate.
吸収後の二酸化炭素の脱離時の温度は90～130℃の範囲が例示される。もちろん、二酸化炭素脱離時の温度が上昇するに従い、二酸化炭素脱離量及び二酸化炭素脱離速度もさらに向上する。二酸化炭素脱離時の圧力は通常ほぼ大気圧で行われる。脱離性能を高めるためより低い圧力まで減圧することもできるが、減圧のために要するエネルギー消費を抑えるため大気圧下で行うのが好ましい。
The temperature at the time of desorption of carbon dioxide after absorption is exemplified by a range of 90 to 130 ° C. Of course, as the temperature at the time of carbon dioxide desorption increases, the carbon dioxide desorption amount and the carbon dioxide desorption rate are further improved. The pressure during carbon dioxide desorption is usually about atmospheric pressure. Although the pressure can be reduced to a lower pressure in order to enhance the desorption performance, it is preferably performed under atmospheric pressure in order to suppress energy consumption required for the pressure reduction.
二酸化炭素を脱離した後の水溶液は、再び二酸化炭素吸収工程に送られ循環使用される。この間、二酸化炭素脱離工程で加えられた熱は、循環過程において水溶液との熱交換により水溶液の昇温に有効に利用されて回収工程全体のエネルギーの低減が計られる。
The aqueous solution from which carbon dioxide has been desorbed is sent again to the carbon dioxide absorption process and recycled. During this time, the heat applied in the carbon dioxide desorption process is effectively used to increase the temperature of the aqueous solution by heat exchange with the aqueous solution in the circulation process, thereby reducing the energy of the entire recovery process.
このようにして回収された二酸化炭素の純度は、通常、95～99.9体積％程度と極めて純度が高いものである。この純粋な二酸化炭素あるいは高濃度の二酸化炭素は、化学品、高分子物質の合成原料、あるいは食品冷凍用の冷剤等として用いられる。その他、回収した二酸化炭素を、現在技術開発されつつある地下等へ隔離貯蔵することも可能である。
The purity of carbon dioxide recovered in this way is usually extremely high, about 95 to 99.9% by volume. This pure carbon dioxide or high-concentration carbon dioxide is used as a chemical, a raw material for synthesizing a high-molecular substance, or a cooling agent for freezing food. In addition, it is possible to sequester and store the recovered carbon dioxide in the underground, where technology is currently being developed.
次に、本発明について実施例及び比較例を用いて詳細に説明するが、本発明はこの実施例に限定されるものではない。本明細書中において、特に指定しない限り、％とは重量％を示す。なお、以下の実施例で用いた化合物のうちM2PPM、MDEA、IPAE及びPZはいずれも東京化成工業社の試薬を使用し、又E3PPM及び1-メチル-4-ピペリジンメタノール(M4PPM)は前述の文献例記載の方法に従い、対応するピペリジンメタノールのエチル化、又はメチル化により合成した。
Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. In the present specification, unless otherwise specified, “%” means “% by weight”. Of the compounds used in the following examples, M2PPM, MDEA, IPAE and PZ all use reagents from Tokyo Chemical Industry Co., Ltd., and E3PPM and 1-methyl-4-piperidinemethanol (M4PPM) According to the method described in the examples, the corresponding piperidine methanol was synthesized by ethylation or methylation.
なお、二酸化炭素飽和吸収量は、該水溶液中の無機炭素量をガスクロマトグラフ式の全有機炭素計で測定した値であり、また、二酸化炭素吸収速度は、飽和吸収量の1/2の二酸化炭素を吸収した時点において赤外線式二酸化炭素計を用いて測定した値である。
The saturated carbon dioxide absorption is a value obtained by measuring the amount of inorganic carbon in the aqueous solution with a gas chromatographic total organic carbon meter, and the carbon dioxide absorption rate is carbon dioxide that is 1/2 of the saturated absorption. It is a value measured using an infrared carbon dioxide meter at the time of absorbing.
実施例１
液の温度が40℃になるように設定した恒温水槽内に、ガラス製のガス吸収ビンを浸し、これにM2PPMを22重量％、IPAEを25重量％及びPZを3重量％含む水溶液50 mlを充填した。この液の中に、目の粗さ100 μm、直径13 mmのガラスフィルターを通して、大気圧下、0.7 L/分で二酸化炭素20体積％及びN280体積％を含む混合ガスを泡状に分散させて吸収させた。 Example 1
A glass gas absorption bottle is immersed in a constant-temperature water bath set to a temperature of 40 ° C, and 50 ml of an aqueous solution containing 22% by weight of M2PPM, 25% by weight of IPAE and 3% by weight of PZ is placed in this bottle. Filled. A mixed gas containing 20% by volume of carbon dioxide and 80% by volume of N 2 at a pressure of 0.7 L / min is dispersed in a foam form through this glass filter with a coarseness of 100 μm and a diameter of 13 mm. And absorbed.
液の温度が40℃になるように設定した恒温水槽内に、ガラス製のガス吸収ビンを浸し、これにM2PPMを22重量％、IPAEを25重量％及びPZを3重量％含む水溶液50 mlを充填した。この液の中に、目の粗さ100 μm、直径13 mmのガラスフィルターを通して、大気圧下、0.7 L/分で二酸化炭素20体積％及びN280体積％を含む混合ガスを泡状に分散させて吸収させた。 Example 1
A glass gas absorption bottle is immersed in a constant-temperature water bath set to a temperature of 40 ° C, and 50 ml of an aqueous solution containing 22% by weight of M2PPM, 25% by weight of IPAE and 3% by weight of PZ is placed in this bottle. Filled. A mixed gas containing 20% by volume of carbon dioxide and 80% by volume of N 2 at a pressure of 0.7 L / min is dispersed in a foam form through this glass filter with a coarseness of 100 μm and a diameter of 13 mm. And absorbed.
水溶液入口及び水溶液出口のガス中の二酸化炭素濃度を、赤外線式の二酸化炭素計(HORIBA GAS ANALYZER VA-3000)で連続的に測定して、入口及び出口の二酸化炭素流量の差から二酸化炭素吸収量を測定した。必要により水溶液中の無機炭素量をガスクロマトグラフ式の全有機炭素計(SHIMADZU TOC-VCSH)で測定し、赤外線式二酸化炭素計から算出される値と比較した。飽和吸収量は水溶液出口の二酸化炭素濃度が入口の二酸化炭素濃度に一致する時点における量とした。吸収速度は飽和吸収量の1/2を吸収した時点の吸収速度で比較することとした。二酸化炭素飽和吸収量は148 g/Lで、飽和吸収量の1/2吸収時の吸収速度は5.0 g/L/minであった。
The carbon dioxide concentration in the gas at the aqueous solution inlet and the aqueous solution outlet is continuously measured with an infrared carbon dioxide meter (HORIBA GAS ANALYZER VA-3000). Was measured. If necessary, the amount of inorganic carbon in the aqueous solution was measured with a gas chromatographic total organic carbon meter (SHIMADZU-TOC-VCSH) and compared with the value calculated from an infrared carbon dioxide meter. The saturated absorption amount was the amount at the time when the carbon dioxide concentration at the outlet of the aqueous solution coincided with the carbon dioxide concentration at the inlet. The absorption rate was compared with the absorption rate at the time when 1/2 of the saturated absorption amount was absorbed. The saturated absorption of carbon dioxide was 148 g / L, and the absorption rate at half absorption of the saturated absorption was 5.0 g / L / min.
ついで同じガス気流中で液温を数分にて70℃に上げて、液からの二酸化炭素脱離量を測定した結果、56 g/Lであった。又、試験例１に示した方法により測定した反応熱は72 kJ/モルCO2であった。
Subsequently, the liquid temperature was raised to 70 ° C. in several minutes in the same gas stream, and the amount of carbon dioxide desorbed from the liquid was measured. As a result, it was 56 g / L. The reaction heat measured by the method shown in Test Example 1 was 72 kJ / mol CO 2 .
実施例2～6
実施例１と同じ装置を用い、同条件でM2PPM、E3PPM、HEPP、HEPL、IPAE及びPZを表１に記載の濃度で含む水溶液を用いて二酸化炭素吸収時の反応熱、飽和吸収量、吸収速度と二酸化炭素脱離量の測定を行った。得られた結果を表１に示した。なお、表1において〔I〕は本発明に基づく3級アミンの、〔II〕はアルカノールアミン類の、〔III〕はピペラジン類の組成名及び重量%を示す。 Examples 2-6
Using the same apparatus as in Example 1, under the same conditions, heat of reaction, saturated absorption, absorption rate at the time of carbon dioxide absorption using an aqueous solution containing M2PPM, E3PPM, HEPP, HEPL, IPAE, and PZ at the concentrations shown in Table 1 And the amount of carbon dioxide desorption was measured. The obtained results are shown in Table 1. In Table 1, [I] represents the composition of the tertiary amine according to the present invention, [II] represents the alkanolamine, and [III] represents the piperazine composition name and weight%.
実施例１と同じ装置を用い、同条件でM2PPM、E3PPM、HEPP、HEPL、IPAE及びPZを表１に記載の濃度で含む水溶液を用いて二酸化炭素吸収時の反応熱、飽和吸収量、吸収速度と二酸化炭素脱離量の測定を行った。得られた結果を表１に示した。なお、表1において〔I〕は本発明に基づく3級アミンの、〔II〕はアルカノールアミン類の、〔III〕はピペラジン類の組成名及び重量%を示す。 Examples 2-6
Using the same apparatus as in Example 1, under the same conditions, heat of reaction, saturated absorption, absorption rate at the time of carbon dioxide absorption using an aqueous solution containing M2PPM, E3PPM, HEPP, HEPL, IPAE, and PZ at the concentrations shown in Table 1 And the amount of carbon dioxide desorption was measured. The obtained results are shown in Table 1. In Table 1, [I] represents the composition of the tertiary amine according to the present invention, [II] represents the alkanolamine, and [III] represents the piperazine composition name and weight%.
比較例1～3
実施例１と同じ装置を用い、同条件でMDEA、M4PPM、IPAE及びPZを表２に記載の濃度で含む水溶液を用いて二酸化炭素吸収時の反応熱、飽和吸収量、吸収速度と二酸化炭素脱離量の測定を行った。得られた結果を表２に示した。 Comparative Examples 1 to 3
Using the same equipment as in Example 1 and using the aqueous solution containing MDEA, M4PPM, IPAE and PZ at the concentrations shown in Table 2 under the same conditions, the reaction heat at the time of carbon dioxide absorption, saturated absorption amount, absorption rate and carbon dioxide desorption The amount of separation was measured. The obtained results are shown in Table 2.
実施例１と同じ装置を用い、同条件でMDEA、M4PPM、IPAE及びPZを表２に記載の濃度で含む水溶液を用いて二酸化炭素吸収時の反応熱、飽和吸収量、吸収速度と二酸化炭素脱離量の測定を行った。得られた結果を表２に示した。 Comparative Examples 1 to 3
Using the same equipment as in Example 1 and using the aqueous solution containing MDEA, M4PPM, IPAE and PZ at the concentrations shown in Table 2 under the same conditions, the reaction heat at the time of carbon dioxide absorption, saturated absorption amount, absorption rate and carbon dioxide desorption The amount of separation was measured. The obtained results are shown in Table 2.
表１に示されるように、本発明による3級アミンは従来から知られている代表的な3級アミンであるMDEAと比較して反応熱は勿論のこと、吸収反応速度、飽和吸収量のいずれに於いても優れており、これらのアミンの特異的な高性能が確認できた。
As shown in Table 1, the tertiary amine according to the present invention has not only the heat of reaction but also the absorption reaction rate and the saturated absorption amount as compared with MDEA, which is a typical tertiary amine conventionally known. The specific high performance of these amines was confirmed.
又、実施例2、3と比較例2の対比で判るようにヒドロキシアルキル基の置換位置により性能に差が見られる。これは前述のように置換位置が窒素原子に対して2,3位のM2PPM、E3PPMでは、プロトン化アミンと水酸基が環状構造をとることによる安定化効果がでるが、M4PPMでは、この2官能基の距離が離れて安定化構造が取れないことによると推定される。
Further, as can be seen from the comparison between Examples 2 and 3 and Comparative Example 2, there is a difference in performance depending on the substitution position of the hydroxyalkyl group. As described above, in M2PPM and E3PPM where the substitution position is 2,3 with respect to the nitrogen atom, a stabilizing effect can be obtained by taking a cyclic structure of the protonated amine and the hydroxyl group. It is estimated that this is due to the fact that the stabilization structure cannot be taken due to the distance of.
又、当該の3級アミンを〔I〕の成分とし、〔II〕の成分としてアルカノールアミン類、〔III〕の成分としてピペラジン類を含む水溶液である実施例4、5及び6に対応した組成の比較例として、従来から3級アミンとして工業的にも使用されているMDEAを含む場合の吸収性能を比較例3に示す。実施例1の場合72 kJ/モルCO2で、現在工業的に使用されているMEAの85 kJ/molCO2よりはるかに低く、本発明の課題とする二酸化炭素の回収エネルギーの低減がなされている。
In addition, the tertiary amine is an aqueous solution containing the tertiary amine as a component [I], an alkanolamine as a component [II], and a piperazine as a component [III]. As a comparative example, Comparative Example 3 shows the absorption performance when MDEA, which has been conventionally used industrially as a tertiary amine, is included. If 72 kJ / mol CO 2 of Example 1, are now industrially of MEA used 85 kJ / molCO 2 much lower than, the reduction of energy recovered carbon dioxide is an object of the present invention is made .
特に、二酸化炭素の吸収時の速度については、実施例4、5及び6とも従来の代表的3級アミンであるMDEAを〔I〕の成分として含む比較例3より速く、工業的に実施する上での大きな利点となることが確認できた。
In particular, the rate at the time of carbon dioxide absorption is higher than that of Comparative Example 3 in which Examples 4, 5, and 6 contain MDEA, which is a conventional representative tertiary amine, as a component of [I]. It was confirmed that this is a great advantage.
試験例１
恒温槽中に設置された同一形状のガラス製反応槽及びリファレンス槽からなる示差熱型反応熱量計（SETARAM社、DRC）を用いて二酸化炭素吸収の反応熱を測定した。反応槽及びリファレンス槽にそれぞれ150 mLの実施例2の水溶液を充填し、槽のジャケット部分に40℃の恒温水を循環させる。この状態で反応槽の水溶液に100％濃度の二酸化炭素ガスを200 ml/分で吹込み、液の温度上昇を二酸化炭素吸収が終了するまで温度記録計にて連続的に記録し、事前に測定された反応槽とジャケット水間の総括伝熱係数を用いて、反応熱を算出した。その結果二酸化炭素吸収の反応熱は58 kJ/molCO2であった。 Test example 1
The reaction heat of carbon dioxide absorption was measured using a differential thermal reaction calorimeter (SETARAM, DRC) consisting of a glass reaction tank and a reference tank of the same shape installed in a thermostat. Each of the reaction tank and the reference tank is filled with 150 mL of the aqueous solution of Example 2, and 40 ° C. constant temperature water is circulated in the jacket portion of the tank. In this state, 100% carbon dioxide gas was blown into the reaction vessel aqueous solution at 200 ml / min, and the temperature rise of the liquid was continuously recorded with a temperature recorder until the carbon dioxide absorption was completed, and measured in advance. The reaction heat was calculated using the overall heat transfer coefficient between the reaction tank and the jacket water. Reaction heat resulting carbon dioxide absorption was 58 kJ / molCO 2.
恒温槽中に設置された同一形状のガラス製反応槽及びリファレンス槽からなる示差熱型反応熱量計（SETARAM社、DRC）を用いて二酸化炭素吸収の反応熱を測定した。反応槽及びリファレンス槽にそれぞれ150 mLの実施例2の水溶液を充填し、槽のジャケット部分に40℃の恒温水を循環させる。この状態で反応槽の水溶液に100％濃度の二酸化炭素ガスを200 ml/分で吹込み、液の温度上昇を二酸化炭素吸収が終了するまで温度記録計にて連続的に記録し、事前に測定された反応槽とジャケット水間の総括伝熱係数を用いて、反応熱を算出した。その結果二酸化炭素吸収の反応熱は58 kJ/molCO2であった。 Test example 1
The reaction heat of carbon dioxide absorption was measured using a differential thermal reaction calorimeter (SETARAM, DRC) consisting of a glass reaction tank and a reference tank of the same shape installed in a thermostat. Each of the reaction tank and the reference tank is filled with 150 mL of the aqueous solution of Example 2, and 40 ° C. constant temperature water is circulated in the jacket portion of the tank. In this state, 100% carbon dioxide gas was blown into the reaction vessel aqueous solution at 200 ml / min, and the temperature rise of the liquid was continuously recorded with a temperature recorder until the carbon dioxide absorption was completed, and measured in advance. The reaction heat was calculated using the overall heat transfer coefficient between the reaction tank and the jacket water. Reaction heat resulting carbon dioxide absorption was 58 kJ / molCO 2.
Claims (7)
- 二酸化炭素を含むガスから二酸化炭素を吸収及び回収するための水溶液であって、一般式〔1〕で表される第3級アミン化合物を少なくとも1種含むことを特徴とする水溶液。
一般式〔1〕：
General formula [1]:
- 一般式〔1〕の第3級アミン化合物が1-メチル-2-ピペリジンメタノール、1-メチル-2-ピペリジンエタノール、1-メチル-3-ピペリジンメタノール、1-エチル-2-ピペリジンメタノール、1-エチル-3-ピペリジンメタノール、1-エチル-2-ピペリジンエタノール、1-(2-ヒドロキシエチル)ピロリジン、1-(2-ヒドロキシエチル)ピペリジン及び1-(3-ヒロキシプロピル)ピロリジンからなる群より選ばれる少なくとも1種である請求項１に記載の水溶液。 The tertiary amine compound of the general formula [1] is 1-methyl-2-piperidinemethanol, 1-methyl-2-piperidineethanol, 1-methyl-3-piperidinemethanol, 1-ethyl-2-piperidinemethanol, 1- From the group consisting of ethyl-3-piperidinemethanol, 1-ethyl-2-piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) piperidine and 1- (3-hydroxypropyl) pyrrolidine The aqueous solution according to claim 1, which is at least one selected.
- 一般式〔1〕の第3級アミン化合物の含有量が5～45重量%である請求項１に記載の水溶液。 The aqueous solution according to claim 1, wherein the content of the tertiary amine compound of the general formula [1] is 5 to 45% by weight.
- 更に、アルカノールアミン類及びピペラジン類からなる群より選ばれる少なくとも1種を含む請求項１に記載の水溶液。 The aqueous solution according to claim 1, further comprising at least one selected from the group consisting of alkanolamines and piperazines.
- アルカノールアミン類が、2-(イソプロピルアミノ)エタノール、2-(エチルアミノ)エタノール及び2-アミノ-2-メチル-1-プロパノールからなる群より選ばれる少なくとも1種である請求項４に記載の水溶液。 The aqueous solution according to claim 4, wherein the alkanolamine is at least one selected from the group consisting of 2- (isopropylamino) ethanol, 2- (ethylamino) ethanol and 2-amino-2-methyl-1-propanol. .
- ピペラジン類が、ピペラジン、2-メチルピペラジン及び2,6-ジメチルピペラジンからなる群より選ばれる少なくとも1種である請求項４に記載の水溶液。 The aqueous solution according to claim 4, wherein the piperazine is at least one selected from the group consisting of piperazine, 2-methylpiperazine and 2,6-dimethylpiperazine.
- （１）請求項１に記載の水溶液に接触させて該水溶液に二酸化炭素を吸収させる工程、及び
（２）上記（１）で得られた二酸化炭素が吸収された水溶液を加熱して、二酸化炭素を脱離して回収する工程、
を含む二酸化炭素の吸収及び回収方法。 (1) a step of bringing the aqueous solution into contact with the aqueous solution according to claim 1 and absorbing the carbon dioxide in the aqueous solution; and (2) heating the aqueous solution in which the carbon dioxide obtained in (1) is absorbed, Removing and recovering
Carbon dioxide absorption and recovery method comprising:
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| WO2014087075A1 (en) | 2012-12-07 | 2014-06-12 | IFP Energies Nouvelles | Absorbent solution made from amines belonging to the n-alkyl-hydroxypiperidine family and method for eliminating acid compounds from a gaseous effluent with such a solution |
| US9409119B2 (en) | 2010-12-22 | 2016-08-09 | Kabushiki Kaisha Toshiba | Acid gas absorbent, acid gas removal method, and acid gas removal device |
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| JP5215595B2 (en) | 2007-06-18 | 2013-06-19 | 三菱重工業株式会社 | Absorbing liquid, CO2 or H2S removing apparatus and method using absorbing liquid |
| EP2259863B1 (en) * | 2008-04-01 | 2013-09-18 | Commonwealth Scientific and Industrial Research Organisation | Improved alkanolamines for co2 removal from gas streams |
| PL2391435T3 (en) * | 2009-02-02 | 2014-05-30 | Basf Se | Absorbing composition comprising cyclic amines for removal of acid gas |
| EP3653584A1 (en) | 2010-02-10 | 2020-05-20 | Queen's University At Kingston | Water with switchable ionic strength |
| MX363651B (en) * | 2010-12-15 | 2019-03-28 | Univ Kingston | Systems and methods for use of water with switchable ionic strength. |
| JP5659127B2 (en) * | 2010-12-22 | 2015-01-28 | 株式会社東芝 | Acid gas absorbent, acid gas removal method, and acid gas removal apparatus |
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| KR101861780B1 (en) | 2014-12-31 | 2018-05-28 | 서울대학교산학협력단 | Controlling system for CO2 absorption and release using temperature-sensitive materials and osmotic pressure control by the system, water desalination and water purification using the draw solute |
| JP6860147B2 (en) * | 2016-09-08 | 2021-04-14 | 株式会社Ihi | Absorbents and absorbents for substituted piperazine compounds and acid gases |
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| JP2006167520A (en) * | 2004-12-13 | 2006-06-29 | Mitsubishi Heavy Ind Ltd | Absorbing liquid and apparatus and method for removing carbon dioxide or hydrogen sulfide in gas by using absorbing liquid |
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| US9409119B2 (en) | 2010-12-22 | 2016-08-09 | Kabushiki Kaisha Toshiba | Acid gas absorbent, acid gas removal method, and acid gas removal device |
| WO2014087075A1 (en) | 2012-12-07 | 2014-06-12 | IFP Energies Nouvelles | Absorbent solution made from amines belonging to the n-alkyl-hydroxypiperidine family and method for eliminating acid compounds from a gaseous effluent with such a solution |
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