TWI614215B - Process of manufaturing carbon capturing agent at moderate/high temperature - Google Patents
Process of manufaturing carbon capturing agent at moderate/high temperature Download PDFInfo
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- TWI614215B TWI614215B TW101130731A TW101130731A TWI614215B TW I614215 B TWI614215 B TW I614215B TW 101130731 A TW101130731 A TW 101130731A TW 101130731 A TW101130731 A TW 101130731A TW I614215 B TWI614215 B TW I614215B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 11
- 230000008569 process Effects 0.000 title abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 15
- CWDGUDXMEXCVBN-UHFFFAOYSA-L aluminum;calcium;carbonate Chemical compound [Al+3].[Ca+2].[O-]C([O-])=O CWDGUDXMEXCVBN-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000011229 interlayer Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- 239000008187 granular material Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010298 pulverizing process Methods 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims description 46
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical group [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 5
- 239000001639 calcium acetate Substances 0.000 claims description 5
- 235000011092 calcium acetate Nutrition 0.000 claims description 5
- 229960005147 calcium acetate Drugs 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009885 systemic effect Effects 0.000 abstract description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 18
- 239000000292 calcium oxide Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- -1 etc. Inorganic materials 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229940118662 aluminum carbonate Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- MIPRAJVRZQTUQX-UHFFFAOYSA-K aluminum;calcium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Al+3].[Ca+2].[O-]C([O-])=O MIPRAJVRZQTUQX-UHFFFAOYSA-K 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000012407 engineering method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
一種中高溫捕碳劑鈣鋁碳酸鹽Ca-Al-CO3工程製造方法，其包含有混合、固液分離、乾燥與擠壓、粉碎與輸送及煅燒成型等步驟；係以鈣離子源與硝酸鋁Al(NO3)3之溶液配製出酸液，且以碳酸鈉(Na2CO3)及氫氧化鈉(NaOH)之溶液配製出鹼液，且將酸液與鹼液混合攪拌再經固液分離形成濾餅，並將濾餅藉由乾燥與擠壓裝置獲得顆粒狀材料，之後將顆粒狀材料藉由輸送與粉碎裝置獲得粉末材料，最後將粉末材料進行高溫爐煅燒，使其於煅燒過程中移除層間陰離子與醋酸根，而形成具有高孔隙鈣鋁碳酸鹽奈米層狀複合材料(Ca-Al-CO3)之捕碳劑。藉此，可調控系統性實驗參數，並配合材料於中高溫(400~800℃)時捕捉二氧化碳，而達到製造批次公斤級產量之乾式捕碳劑之功效。 A medium-high temperature carbon capture agent calcium-aluminum carbonate Ca-Al-CO 3 engineering manufacturing method, which comprises the steps of mixing, solid-liquid separation, drying and extrusion, pulverization and transportation, and calcination, etc.; A solution of aluminum Al(NO 3 ) 3 is used to prepare an acid solution, and an alkali solution is prepared by using a solution of sodium carbonate (Na 2 CO 3 ) and sodium hydroxide (NaOH), and the acid solution and the alkali solution are mixed and stirred and then solidified. The liquid is separated to form a filter cake, and the filter cake is obtained by a drying and pressing device to obtain a granular material, and then the granular material is obtained by a conveying and pulverizing device, and finally the powder material is calcined in a high temperature furnace to be calcined. The interlayer anion and acetate are removed during the process to form a carbon trapping agent having a high porosity calcium aluminum carbonate nano layered composite (Ca-Al-CO 3 ). In this way, the systemic experimental parameters can be adjusted, and the carbon dioxide can be captured at medium and high temperatures (400-800 ° C) to achieve the effect of producing dry-type carbon capture agent in batches of kilograms.
Description
本發明係有關於一種中高溫捕碳劑鈣鋁碳酸鹽Ca-Al-CO3工程製造方法，尤指一種可調控系統性實驗參數，並配合材料於中高溫(400~800℃)時捕捉二氧化碳，而達到製造批次公斤級產量之乾式捕碳劑之功效。 The invention relates to a medium-high temperature carbon capture agent calcium-aluminum carbonate Ca-Al-CO 3 engineering manufacturing method, in particular to a systemic experimental parameter which can be adjusted and used to capture carbon dioxide at medium and high temperature (400~800 ° C). And achieve the efficacy of the dry carbon capture agent for the production of batches of kilograms.
利用二氧化碳(CO2)捕捉技術達成二氧化碳減量為國際共同努力目標之一，並能廣泛用於工業上與CO2排放有關的高溫程序如燃燒煤、石油、天然氣吸附加強重組(Adsorption enhanced reforming,AER)等。國際經驗顯示目前較為廣泛應用之捕碳技術為燃燒後(Postcombustion)捕碳，常用如醇胺液於100~150℃程序。此類型捕碳技術存在有低捕碳量、高耗能、具腐蝕性等環境不利缺點。此外，適用溫度較窄亦為另一重要考量。由於全球急待減緩有關CO2溫室效應，因此廣泛開發CO2捕獲技術以因應不同產業應用必成為趨勢。例如美國能源部將乾式固態捕碳劑(Solid sorbent)列為未來10年內具有新興潛力技術即可佐證。 The use of carbon dioxide (CO 2 ) capture technology to achieve carbon dioxide reduction is one of the international joint efforts, and can be widely used in industrial high temperature procedures related to CO 2 emissions such as coal combustion, oil, natural gas adsorption enhanced reorganization (AER) )Wait. International experience shows that the currently widely used carbon capture technology is post-combustion carbon capture, commonly used in alcohol-amine liquids at 100-150 ° C procedures. This type of carbon capture technology has the disadvantages of low carbon capture, high energy consumption, and corrosive environmental disadvantages. In addition, the narrower application temperature is another important consideration. Due to the global urgency to slow down the CO 2 greenhouse effect, the widespread development of CO 2 capture technology in response to different industry applications is a trend. For example, the US Department of Energy listed the dry solid sorbent as a technology with emerging potential in the next 10 years.
捕碳劑技術之主要優點在於適用溫度範圍廣(約室溫~800℃)，使用與處理方便及較為環境友善等。CO2捕捉量與溫度及使用材料有關，Wang(Energy Environ.Sci.,2011,4,3805-3819)比較 不同捕碳劑性能，通常分為3類：(1)低溫(<200℃)，例如碳材料、沸石、胺基amine改質、有機金屬框架(MOFs)、鹼金屬碳酸鹽等，捕碳量3.5-9.4mmol/g。(2)中溫(200-400℃)，例如Mg-Al層狀化合物(LDHs)、K改質LDHs等，捕碳量約1.4mmol/g。(3)高溫(>400℃)，例如含CaO、鹼性陶瓷等，捕碳量6.5-11.6mmol/g。 The main advantage of the carbon capture technology is the wide temperature range (about room temperature ~ 800 ° C), easy to use and handle, and more environmentally friendly. The amount of CO 2 capture is related to temperature and materials used. Wang (Energy Environ. Sci., 2011, 4, 3805-3819) compares the performance of different carbon capture agents and is usually divided into three categories: (1) low temperature (<200 ° C), For example, carbon materials, zeolites, amine-based amine modifications, organometallic frameworks (MOFs), alkali metal carbonates, etc., carbon capture of 3.5-9.4 mmol / g. (2) Medium temperature (200-400 ° C), for example, Mg-Al layered compound (LDHs), K modified LDHs, etc., and the carbon capture amount is about 1.4 mmol/g. (3) High temperature (>400 ° C), for example, containing CaO, alkaline ceramics, etc., carbon capture amount of 6.5-11.6 mmol / g.
各類型捕碳劑有其適用範圍，通常低溫捕碳基於物理性吸附，因此氣體選擇性較差，；而捕碳量之提升則與載體(Support)種類有關，例如結構材料MCM-41、SBA-15、MOF等。結合鹼性基與載體以增加其選擇性與吸附量有其優點，李(中華民國專利申請號098107986)利用胺改質中孔矽基材(MSPs)，可操作於20-150℃，最大吸附量102mg/g(2.32mmol/g)。中溫捕碳劑以MgO系列為主，通常需利用改質提高其性能。韓(J.Hazard.Mater.,2012,203,341-347)在中孔洞基材利用MgO改質，可操作於150-400℃，最大吸附量131mg/g(2.98mmol/g)。 Various types of carbon-trapping agents have their applicability. Generally, low-temperature carbon capture is based on physical adsorption, so the gas selectivity is poor. The increase in carbon capture is related to the type of support, such as structural materials MCM-41, SBA- 15, MOF and so on. Combining the basic group with the carrier to increase its selectivity and adsorption capacity, Li (Republic of China Patent Application No. 098107986) utilizes amine modified mesoporous substrates (MSPs), which can be operated at 20-150 ° C, maximum adsorption The amount was 102 mg/g (2.32 mmol/g). The medium temperature carbon capture agent is mainly based on the MgO series, and it is usually necessary to use the modification to improve its performance. Han (J. Hazard. Mater., 2012, 203, 341-347) is modified with MgO in a mesoporous substrate, and can be operated at 150-400 ° C, and the maximum adsorption amount is 131 mg / g (2.98 mmol / g).
理想的捕碳劑在高溫條件須具備高捕碳量、高速率、穩定性及機械強度等主要條件。高溫捕獲程序具有高CO2濃度、高捕碳量及低能耗之主要優點，實為極具有潛力之技術。此類以含氧化鈣(CaO)系列材料最為廣泛研究，主要包含碳酸化(Carbonation)與再生(Regeneration)步驟。 The ideal carbon capture agent must have high conditions such as high carbon capture, high rate, stability and mechanical strength at high temperatures. The high-temperature capture program has the main advantages of high CO 2 concentration, high carbon capture and low energy consumption, making it a highly promising technology. This type of material is most widely studied in the series containing calcium oxide (CaO), mainly including carbonation and regeneration.
國際現況之技術瓶頸為高溫穩定性有待突破，因此，在高CO2濃度如何維持穩定性為重點；由於高溫與高CO2濃度更易加速材料之劣化，因此大部分研究與專利多屬於燃燒後捕獲。例如：『美國專利申請號US20120025134Al』，其係於合成CaO/MgO系列材料在800-900℃轉化率>90%可維持600min(15%CO2)；或『中華民國專利申請號099116724』，其係利用CaO等金屬氧化物於二氧化碳 捕獲系統，650℃獲得99-100%CO2移除率(13-16%CO2)。以上述之技術而言，其高溫捕碳針對小於16%CO2，所以其並無法提供大量生產，而有不具經濟效益之缺失。 The technical bottleneck of the current international situation is that high temperature stability needs to be broken. Therefore, it is important to maintain stability in high CO 2 concentration. Because high temperature and high CO 2 concentration are more likely to accelerate the deterioration of materials, most of the research and patents belong to post-combustion capture. . For example: "US Patent Application No. US20120025134 Al", which is a synthetic CaO/MgO series material with a conversion rate of >90% at 800-900 ° C for 600 min (15% CO 2 ); or "Republic of China Patent Application No. 099116724", A metal oxide such as CaO was used in a carbon dioxide capture system to obtain a 99-100% CO 2 removal rate (13-16% CO 2 ) at 650 °C. In terms of the above technology, its high temperature carbon capture is less than 16% CO 2 , so it does not provide mass production, and there is no economic benefit.
然，本發明擬利用共沉澱技術建立捕碳劑之工程製造方法與裝置，以獲得公斤級產量之捕碳劑。此材料係由鈣、鋁雙離子藉由氫氧基與碳酸鹽形成之層狀結構，經煅燒後可獲得高CaO含量之無機材料。應用於中高溫(400-800℃)與大濃度範圍(5-100%CO2)捕碳研究將具有前景與利基。 However, the present invention intends to use a coprecipitation technique to establish an engineering manufacturing method and apparatus for a carbon capture agent to obtain a carbonaceous agent in a kilogram production. The material is a layered structure formed of calcium and aluminum ions by a hydroxyl group and a carbonate, and is calcined to obtain an inorganic material having a high CaO content. Carbon sequestration studies for medium to high temperature (400-800 ° C) and large concentration range (5-100% CO 2 ) will have prospects and niches.
本發明之主要目的係在於，可調控系統性實驗參數，並配合材料於中高溫(400~800℃)時捕捉二氧化碳，而達到批次製造公斤級產量之乾式捕碳劑之功效。 The main object of the present invention is to control systemic experimental parameters and to match the material to capture carbon dioxide at medium and high temperatures (400-800 ° C), and to achieve the effect of dry-type carbon capture agent in batch production of kilograms.
為達以上之目的，本發明係一種中高溫捕碳劑鈣鋁碳酸鹽Ca-Al-CO3工程製造方法，其至少包含下列步驟：混合：以鈣離子源與硝酸鋁Al(NO3)3之溶液配製出酸液，且以碳酸鈉(Na2CO3)及氫氧化鈉(NaOH)之溶液配製出鹼液。 For the purpose of the above, the present invention is a medium-high temperature carbon capture agent calcium-aluminum carbonate Ca-Al-CO 3 engineering manufacturing method, which comprises at least the following steps: mixing: a source of calcium ions and aluminum nitrate Al(NO 3 ) 3 The solution is prepared as an acid solution, and a lye is prepared as a solution of sodium carbonate (Na 2 CO 3 ) and sodium hydroxide (NaOH).
固液分離：將酸液與鹼液攪拌形成沉澱，並經固液分離形成濾餅。 Solid-liquid separation: The acid solution is stirred with an alkali solution to form a precipitate, and separated by solid-liquid separation to form a filter cake.
乾燥與擠壓：將濾餅藉由乾燥與擠壓裝置獲得顆粒狀材料。 Drying and Extrusion: The filter cake is obtained by means of a drying and pressing device.
粉碎與輸送：將顆粒狀材料藉由輸送與粉碎裝置獲得粉末材料。 Crushing and conveying: The granular material is obtained by conveying and pulverizing means.
煅燒成型：將粉末材料進行高溫爐煅燒，使其於煅燒過程中移除層間陰離子與醋酸根，而形成具有高孔隙鈣鋁碳酸鹽奈米層狀複 合材料(Ca-Al-CO3)之捕碳劑。 Calcination: The powder material is calcined in a high-temperature furnace to remove interlayer anions and acetate during calcination to form a high-porosity calcium-aluminum carbonate nano-layer composite (Ca-Al-CO 3 ). Carbon agent.
於本發明之一實施例中，該混合步驟中所提鈣離子源係為醋酸鈣Ca(CH3COO)2．xH2O、硝酸鈣Ca(NO3)2、或氯化鈣CaCl2。 In one embodiment of the present invention, the source of calcium ions extracted in the mixing step is calcium acetate Ca(CH 3 COO) 2 . xH 2 O, calcium nitrate Ca(NO 3 ) 2 , or calcium chloride CaCl 2 .
於本發明之一實施例中，該混合步驟中所提鈣離子源與硝酸鋁Al(NO3)3之莫耳比係可介於1：1~30：1之間。 In an embodiment of the present invention, the molar ratio of the calcium ion source and the aluminum nitrate Al(NO 3 ) 3 in the mixing step may be between 1:1 and 30:1.
於本發明之一實施例中，該煅燒成型之步驟中係可在介於400~800℃中高溫範圍捕捉二氧化碳，起始捕碳量10-70wt%。 In an embodiment of the present invention, in the calcining step, carbon dioxide is captured in a high temperature range of 400 to 800 ° C, and the initial carbon capture amount is 10 to 70 wt%.
於本發明之一實施例中，該煅燒成型之步驟中所得之Ca-Al-CO3捕碳劑係可用在CO2濃度5-100%濃度。 In an embodiment of the present invention, the Ca-Al-CO3 carbon capture agent obtained in the calcination step can be used at a concentration of 5-100% of the CO 2 concentration.
於本發明之一實施例中，該煅燒成型之步驟中所得之Ca-Al-CO3捕碳劑經過40-100次迴路(60-150小時)後，其穩定性係高達90-95%以上。 In one embodiment of the present invention, the Ca-Al-CO3 carbon capture agent obtained in the calcination step has a stability of up to 90-95% after 40-100 cycles (60-150 hours).
1‧‧‧混合 1‧‧‧mix
2‧‧‧固液分離 2‧‧‧Solid-liquid separation
3‧‧‧乾燥與擠壓 3‧‧‧Drying and extrusion
4‧‧‧粉碎與輸送 4‧‧‧Smashing and conveying
5‧‧‧煅燒成型 5‧‧‧ calcination
第1圖，係本發明之捕碳劑工程製造方法流程示意圖。 Fig. 1 is a schematic flow chart showing the method of manufacturing a carbon capture agent according to the present invention.
第2圖，係本發明之製造方法利用其中1種前驅物：Ca(CH3COO)2或CaCl2或Ca(NO3)2之捕碳劑在TGA測試10迴路熱重吸附圖。 Fig. 2 is a diagram showing the 10th loop thermoresorption diagram of the TGA test using the carbon capture agent of one of the precursors: Ca(CH 3 COO) 2 or CaCl 2 or Ca(NO 3 ) 2 .
第3圖，係本發明之捕碳劑製造顆粒(上)與粉末(下)表面SEM圖。 Fig. 3 is a SEM image showing the surface (top) and powder (bottom) of the carbon-trapping agent of the present invention.
第4圖，係本發明之Ca：Al=7：1捕碳劑在未煅燒(Uncalcined)及600℃煅燒(Calcined)之XRD圖。 Figure 4 is an XRD pattern of the Ca:Al = 7:1 carbon capture agent of the present invention in Uncalcined and calcined at 600 °C.
第5圖，係本發明之不同比例Ca：Al=1~30：1合成CO22捕獲劑材料基 本性質。 Figure 5 is a graph showing the basic properties of the CO 22 capture agent material in different ratios of Ca: Al = 1 to 30:1 of the present invention.
第6圖，係本發明之Ca：Al=1~30：1不同比例合成捕碳劑與不同材料在室溫~950℃利用TGA測試吸附/脫附CO2隨溫度變化圖。 Figure 6 is a graph showing the adsorption/desorption of CO 2 with temperature in a Ca:Al=1~30:1 synthetic carbon capture agent and different materials at room temperature to 950 °C.
第7圖，係本發明之Ca：Al=7：1捕碳劑在室溫~950℃利用TGA測試5-100%CO2隨溫度變化圖。 Figure 7 is a graph showing the change of 5-100% CO 2 with temperature by the TGA test of the Ca:Al=7:1 carbon trapping agent of the present invention at room temperature to 950 °C.
第8圖，係本發明之Ca：Al=1、5、7、13、20、30捕碳劑在750℃利用TGA測試吸附/脫附CO2之10次迴路穩定性與特性值。 Fig. 8 is a 10th cycle stability and characteristic value of the Ca:Al=1,5,7,13,20,30 carbon trapping agent of the present invention at 750 °C using TGA to test adsorption/desorption of CO 2 .
第9圖，係本發明之Ca：Al=7：1捕碳劑顆粒、粉末與CaO、CaCO3、Limestone、Li4SiO4等材料在650~750℃利用TGA測試吸附/脫附CO2之40次迴路捕碳量(上)與穩定性(下)圖。 Figure 9, is a Ca:Al=7:1 carbon-trapping agent particle, powder and CaO, CaCO 3 , Limestone, Li 4 SiO 4 and the like at 650-750 ° C using TGA to test adsorption/desorption of CO 2 40 times of carbon capture (top) and stability (bottom).
第10圖，係本發明之Ca：Al=7：1捕碳劑顆粒與粉末在750℃利用TGA測試吸附/脫附CO2之100次迴路捕碳量。 Fig. 10 is a graph showing the carbon capture amount of 100 times of the adsorption/desorption of CO 2 by Ca:Al=7:1 carbon-trapping agent particles and powder at 750 ° C using the TGA test.
請參閱『第1圖』所示，係本發明之捕碳劑製造方法流程示意圖。如圖所示：本發明係一種中高溫捕碳劑鈣鋁碳酸鹽Ca-Al-CO3工程製造方法，其至少包括下列步驟： Please refer to FIG. 1 , which is a schematic flow chart of the method for manufacturing a carbon capture agent of the present invention. As shown in the figure: The present invention is a medium-high temperature carbon capture agent calcium-aluminum carbonate Ca-Al-CO 3 engineering manufacturing method, which comprises at least the following steps:
混合1：以鈣離子源與硝酸鋁Al(NO3)3之溶液配製出酸液，且以碳酸鈉(Na2CO3)及氫氧化鈉(NaOH)之溶液配製出鹼液；其中該鈣離子源係為醋酸鈣Ca(CH3COO)2．xH2O、硝酸鈣Ca(NO3)2、或氯化鈣CaCl2，且鈣離子源與硝酸鋁Al(NO3)3之莫耳比係可介於1：1~30：1之間。 Mixing 1: preparing an acid solution by using a solution of calcium ion source and aluminum nitrate Al(NO 3 ) 3 , and preparing a lye solution with a solution of sodium carbonate (Na 2 CO 3 ) and sodium hydroxide (NaOH); wherein the calcium The ion source is calcium acetate Ca(CH 3 COO) 2 . xH 2 O, calcium nitrate Ca(NO 3 ) 2 , or calcium chloride CaCl 2 , and the molar ratio of the calcium ion source to the aluminum nitrate Al(NO 3 ) 3 may be between 1:1 and 30:1. .
固液分離2：將酸液與鹼液攪拌形成沉澱，並經固液分離形成濾 餅。 Solid-liquid separation 2: The acid and the lye are stirred to form a precipitate, which is separated by solid-liquid separation. cake.
乾燥與擠壓3：將濾餅藉由乾燥與擠壓裝置獲得顆粒狀材料。 Drying and Extrusion 3: The filter cake is obtained by means of a drying and pressing device.
粉碎與輸送4：將顆粒狀材料藉由輸送與粉碎裝置獲得粉末材料。 Crushing and conveying 4: A granular material is obtained by a conveying and pulverizing device.
煅燒成型5：將粉末材料進行高溫爐煅燒，使其於煅燒過程中移除層間陰離子與醋酸根，而形成具有高孔隙鈣鋁碳酸鹽奈米層狀複合材料(Ca-Al-CO3)之捕碳劑；然本步驟中係可在介於400~800℃中高溫範圍捕捉二氧化碳，起始捕碳量10-70wt%，且可用在CO2濃度5-100%濃度，而經過40-100次迴路(60-150小時)穩定性高達90-95%以上。 Calcination molding 5: The powder material is calcined in a high-temperature furnace to remove interlayer anions and acetate during calcination to form a high-porosity calcium-aluminum carbonate nano-layer composite (Ca-Al-CO 3 ). Carbon capture agent; in this step, carbon dioxide can be captured in the high temperature range of 400-800 ° C, the initial carbon capture amount is 10-70 wt%, and can be used in the CO 2 concentration 5-100% concentration, and after 40-100 The secondary circuit (60-150 hours) has a stability of over 90-95%.
由於該捕碳劑係利用不同鈣離子來源、硝酸鋁(Al(NO3)3)及碳酸鈉(Na2CO3)作為反應物，加入氫氧化鈉(NaOH)控制鹼性，俾以產生不同比例鈣/鋁碳酸鹽層狀材料，其中該鈣/鋁碳酸鹽層狀材料係為具有兩種金屬陽離子且於其層間結構中含陰離子物種之層狀雙氫氧化物(Layered Double Hydroxides,LDH)，係以鈣(Ca)、鋁(Al)金屬陽離子形成同一層氧化物八面體，並於其層間結構中由碳酸根(CO3 2-)、氫氧根(OH-)構成為其結構特性者，俾利用此種結構作為模板(Template)，經煅燒過程移除層間陰離子與醋酸根，提供合成具有高孔隙之鈣鋁碳酸鹽奈米層狀複合材料(Ca-Al-CO3)，且由於該高孔隙之鈣鋁碳酸鹽奈米層狀複合材料(Ca-Al-CO3)具有高於50wt%之起始捕碳量轉化率，且經過多次捕碳/再生/捕碳循環後仍高達90%之轉化率者，使本發明可製造達批次公斤級產量，具有中高溫大量捕捉或分離 二氧化碳之應用潛能。 Since the carbon capture agent uses different sources of calcium ions, aluminum nitrate (Al(NO 3 ) 3 ) and sodium carbonate (Na 2 CO 3 ) as reactants, sodium hydroxide (NaOH) is added to control the alkalinity, and the mixture is produced to produce different a ratio of calcium/aluminum carbonate layered material, wherein the calcium/aluminum carbonate layered material is a layered double hydroxides (LDH) having two metal cations and an anionic species in its interlayer structure The same layer of oxide octahedron is formed by calcium (Ca) and aluminum (Al) metal cations, and its structure is composed of carbonate (CO 3 2- ) and hydroxide (OH - ) in its interlayer structure. Characteristic, 俾Using this structure as a template, removing interlayer anions and acetate by calcination process, providing synthesis of calcium-aluminum carbonate nano-layered composite material (Ca-Al-CO 3 ) with high porosity, And because the high-porosity calcium aluminum carbonate nano-layered composite material (Ca-Al-CO 3 ) has an initial carbon capture conversion rate of more than 50 wt%, and has undergone multiple carbon capture/regeneration/carbon capture cycles. After the conversion rate of up to 90%, the invention can produce batches of kilograms of production, with medium and high temperature mass capture The potential to capture or separate carbon dioxide.
本發明之製造方法可適用於不同鈣離子來源，例如『第2圖』為利用本發明方法與裝置以Ca(CH3COO)2、CaCl2、Ca(NO3)2等Ca+2來源製造Ca：Al=7：1之Ca-Al-CO3捕碳劑，在熱重分析儀(Thermogravimetric Analyzer,TGA)進行10迴路捕獲CO2實驗。結果顯示3種材料之穩定性皆大於90%，其中以醋酸鈣Ca(CH3COO)2來源之捕碳量與穩定性俱佳，本發明擬以醋酸鈣作為含鈣起始材料來說明合成CO2捕獲劑特性及性能。 The manufacturing method of the present invention can be applied to different sources of calcium ions. For example, "Fig. 2" is a method for manufacturing a Ca + 2 source such as Ca(CH 3 COO) 2 , CaCl 2 or Ca(NO 3 ) 2 by the method and apparatus of the present invention. Ca: Al = 7:1 Ca-Al-CO 3 carbon capture agent, and a 10 loop capture CO 2 experiment was performed on a Thermogravimetric Analyzer (TGA). The results show that the stability of all three materials is more than 90%, among which the carbon capture amount and stability of calcium acetate Ca(CH 3 COO) 2 source are excellent. The present invention intends to use calcium acetate as the calcium-containing starting material to illustrate the synthesis. CO 2 capture agent characteristics and properties.
『第3圖』係藉由本發明裝置獲得之捕碳劑圖例，舉例如顆粒(上)與粉末(下)捕碳劑表面SEM圖。其中顆粒(Granule)代表尺寸為直徑2-3mm與長度3-5mm圓柱型外觀，粉末(Powder)表面形貌近似片狀且為層疊分佈，聚集尺寸分佈約100-200um。因此本發明可同時製造粉體與顆粒捕碳劑，應用於固定式或流動式CO2捕獲反應器。 "Fig. 3" is a legend of a carbon trapping agent obtained by the apparatus of the present invention, for example, an SEM image of the surface of the particle (top) and powder (bottom) carbon trapping agent. Granules represent a cylindrical shape with a diameter of 2-3 mm and a length of 3-5 mm. The surface morphology of the powder is approximately sheet-like and is a layered distribution with an aggregate size distribution of about 100-200 um. Therefore, the present invention can simultaneously manufacture a powder and a particulate carbon trapping agent for use in a stationary or mobile CO 2 capture reactor.
『第4圖』係本發明之Ca：Al=7：1捕碳劑在未煅燒(Uncalcined)及600℃煅燒(Calcined)之XRD圖。由此圖顯示本發明材料設計主要概念，係藉由鈣(Ca+2)、鋁(Al+3)陽離子形成同一層氧化物八面體，並由碳酸根(CO3 2-)、氫氧根(OH-)構成其層間結構者，所形成原始結構為層狀雙氫氧化物(Layered Double Hydroxides,LDHs)，其特徵繞射峰(★)如未煅燒(Uncalcined)圖譜，屬於鈣鋁氫氧基與碳酸基之複合物(01-087-0493，Calcium Aluminum Hydroxide Carbonate Hydrate)。此結構經600℃煅燒(Calcined)移除層間陰離子與醋酸根，可增加孔隙度，並形成含有Ca(OH)2、CaCO3、CaO等之Ca-Al碳酸鹽層狀複合材 料Ca-Al-CO3。 "Fig. 4" is an XRD pattern of the Ca:Al = 7:1 carbon trapping agent of the present invention in uncalcined and calcined at 600 °C. The figure shows the main concept of the material design of the present invention, which forms the same layer of oxide octahedron by calcium (Ca + 2 ) and aluminum (Al + 3 ) cations, and is composed of carbonate (CO 3 2- ), hydrogen and oxygen. The root (OH - ) constitutes its interlayer structure, and the original structure formed is Layered Double Hydroxides (LDHs). Its characteristic diffraction peak (★), such as uncalcined spectrum, belongs to calcium aluminum hydrogen. A complex of an oxy group and a carbonate group (01-087-0493, Calcium Aluminum Hydroxide Carbonate Hydrate). This structure is calcined at 600 °C to remove interlayer anions and acetate, which can increase the porosity and form a Ca-Al carbonate layered composite Ca-Al-containing Ca(OH) 2 , CaCO 3 , CaO and the like. CO 3 .
『第5圖』係本發明之不同比例Ca：Al=1~30：1合成Ca-Al-CO3捕碳劑粉末材料基本性質。捕碳劑粉體尺寸可藉由溫度與静置時間控制，使粒徑分佈於10-200um範圍。此材料具有中孔(Mesoporous)特性，表面積10.0-40.0m2/g，孔體積0.02-0.20m2/g，孔徑21.0-40.0nm。CaO含量係將捕碳劑粉末溶解後，利用感應耦合電漿光譜法(Inductively Coupled Plasma,ICP)定量Ca元素含量，並藉以計算所含氧化鈣含量，CaO含量隨較高的Ca：Al比例而增加，其值約40-80wt%。 "Fig. 5" is a basic property of the Ca-Al-CO 3 carbon-trapping powder material of different ratios of Ca: Al = 1 to 30:1 in the present invention. The carbon powder size can be controlled by temperature and standing time to make the particle size distribution in the range of 10-200 um. This material has a mesoporous (Mesoporous) characteristics, surface area 10.0-40.0m 2 / g, a pore volume 0.02-0.20m 2 / g, pore 21.0-40.0nm. After the CaO content is dissolved in the carbon powder, the Ca content is quantified by Inductively Coupled Plasma (ICP), and the calcium oxide content is calculated, and the CaO content is proportional to the higher Ca:Al ratio. Increased, the value is about 40-80% by weight.
利用熱重分析(TGA)測試捕碳劑性能，並以每單位重之捕碳劑在不同溫度吸收CO2增加之重量表示捕碳量wt%(g CO2/g sorbent)。不同捕碳劑測試吸附CO2容量如『第6圖』所示，係本發明之Ca：Al=1~30：1不同比例合成捕碳劑與不同材料，在室溫~950℃利用TGA測試吸附/脫附CO2隨溫度變化圖。結果顯示，在100%,50cc/min CO2實驗條件，Ca-Al-CO3捕碳劑、CaO、CaCO3等粉末可用於400~800℃以上捕捉CO2。藉由改變Ca與Al比例可增加捕碳量，定溫750℃條件Ca：Al=30：1~13：1之起始捕碳量與CaCO3相當，Ca：Al=7：1則近似CaO，Al2O3、Na2CO3則無顯著吸附性能。本發明Ca-Al-CO3系列捕碳劑在定溫750℃之起始捕碳量隨Ca與Al比例增加，當Ca：Al=1~30：1，捕碳量達10-71wt%。 Thermogravimetric analysis (TGA) test carbon capture agent performance and to re-capture of carbon per unit increase of the CO 2 absorption agent at different temperatures are expressed by weight of carbon capture wt% (g CO 2 / g sorbent). Carbon adsorption test agents different collectors CO 2 capacity as shown in "FIG. 6", the present invention based Ca: Al = 1 ~ 30: 1 ratio of different synthetic capture agent to the different carbon materials using TGA test at room temperature ~ 950 ℃ Adsorption/desorption of CO 2 as a function of temperature. The results show that in the 100%, 50 cc / min CO 2 experimental conditions, Ca-Al-CO 3 carbon capture agent, CaO, CaCO 3 and other powders can be used to capture CO 2 above 400 ~ 800 ° C. The carbon capture can be increased by changing the ratio of Ca to Al. The initial carbon capture of Ca:Al=30:1~13:1 is equivalent to CaCO 3 at a fixed temperature of 750 °C, and CaO is similar to Ca:Al=7:1. Al 2 O 3 and Na 2 CO 3 have no significant adsorption properties. The initial carbon capture amount of the Ca-Al-CO 3 series carbon trapping agent at a constant temperature of 750 ° C increases with the ratio of Ca to Al. When Ca:Al=1~30:1, the carbon capture amount is 10-71 wt%.
捕碳劑另一重要性能為可適用於廣範圍CO2濃度變化，以應用於不同工業捕獲程序。美國National Energy Technology Laboratory(NETL)列舉二種常用的CO2捕獲技術：燃燒後(Post combustion)5-15%CO2，燃燒前(Pre-combustion)10-50%CO2濃度 範圍。如『第7圖』以Ca：Al=7：1捕碳劑為例，在室溫~950℃利用TGA測試吸附/脫附CO2隨溫度變化圖，在600℃以上可觀察到明顯吸附性能，當CO2濃度(v/v)：5%、10%、17%、29%、38%、44%、50%、100%在750℃捕碳量(wt%)分別為50.32%、51.41%、51.5%、53.63%、54.26%、55.97%、56.26%、56.88%，此結果顯示本發明捕碳劑可用於5-100%CO2濃度範圍。 Another important property of the carbon capture agent is that it can be applied to a wide range of CO 2 concentration changes for use in different industrial capture procedures. The National Energy Technology Laboratory (NETL) of the United States lists two commonly used CO 2 capture technologies: Post combustion 5-15% CO 2 , Pre-combustion 10-50% CO 2 concentration range. For example, in Figure 7, taking the Ca:Al=7:1 carbon trapping agent as an example, the TGA is used to test the adsorption/desorption of CO 2 with temperature at room temperature ~950 °C. Obvious adsorption performance can be observed above 600 °C. When the CO 2 concentration (v/v): 5%, 10%, 17%, 29%, 38%, 44%, 50%, 100%, the carbon capture amount (wt%) at 750 ° C is 50.32%, 51.41, respectively. %, 51.5%, 53.63%, 54.26%, 55.97%, 56.26%, 56.88%, this result shows that the carbon capture agent of the present invention can be used in the range of 5-100% CO 2 concentration.
當運用時，利用上述合成之捕碳劑在介於400~800℃中高溫範圍捕捉CO2，其捕獲CO2增加重量與原來測試材料重量比例，來計算其捕碳比例wt%。被吸附之CO2與捕碳劑形成CaCO3，在加溫時降低CO2濃度使得捕碳劑再生為具有CO2吸附活性之CaO，其單一捕碳迴路反應式如下：(吸附捕捉1小時)CaO+CO2→CaCO3 When used, the above-mentioned synthetic carbon trapping agent captures CO 2 in a high temperature range of 400 to 800 ° C, and captures the weight ratio of the CO 2 increasing weight to the original test material to calculate the carbon capture ratio wt%. The adsorbed CO 2 forms a CaCO 3 with the carbon trapping agent, and reduces the CO 2 concentration when heating, so that the carbon trapping agent is regenerated into CaO having CO 2 adsorption activity, and the single carbon trapping loop has the following reaction formula: (adsorption capture for 1 hour) CaO+CO 2 →CaCO 3
(脫附再生0.5小時)CaCO3→CaO+CO2 (desorption regeneration for 0.5 hours) CaCO 3 →CaO+CO 2
單1次捕碳迴路(1 Cycle=1.5小時)包含上述吸附與脫附步驟，經過多次捕碳/再生之捕碳循環實驗維持之捕碳比例即為其穩定性。如『第8圖』以不同比例醋酸鈣為例，持溫750℃之捕碳量稍高於第6圖之範圍。Ca：Al=1-30捕碳劑起始捕碳量約為10-70wt%，且捕碳劑經過10次捕碳迴路(15小時)穩定性仍高達90%，顯示在此範圍之高捕碳性能。 The single carbon capture circuit (1 Cycle = 1.5 hours) contains the above adsorption and desorption steps, and the carbon capture ratio maintained by the carbon capture/regeneration carbon capture cycle experiment is the stability. For example, in Figure 8, the ratio of carbon dioxide at a temperature of 750 °C is slightly higher than that of Figure 6. The initial carbon capture of Ca:Al=1-30 carbon capture agent is about 10-70wt%, and the carbon capture agent is still up to 90% after 10 times of carbon capture circuit (15 hours), indicating that it is high in this range. Carbon properties.
國際上乾式CO2捕獲劑適用於不同溫度範圍，在中高溫600℃以上主要以含有CaO、鹼性礦物及鋰矽酸鹽等為最常見。如『第9圖』所示為本發明Ca：Al=7：1捕碳劑顆粒、粉末與CaO、CaCO3、Limestone、Li4SiO4等材料在650~750℃利用TGA測試吸附/脫附 2之40次迴路(60小時)性能比較。結果顯示：(1)在40次迴路測試中，本發明捕碳劑之捕碳量維持在50-55wt%，穩定性至少95-98%。如『第10圖』，即使在100次迴路測試仍高達90%。(2)CaO因純度達95-99%，因此具有較高之捕碳量，但40次迴路穩定性約85-90%，且呈現持續衰退趨勢。(3)Limestone與Li4SiO4等材料之捕碳量約25-45%，40次迴路穩定性約80%。(4)本測試中以CaCO3穩定性較差，其初始捕碳量約65wt%，僅在5-10迴路後即衰退為40-45wt%，穩定性約原來捕碳量60-70%。本發明之捕碳劑經40-100次迴路穩定性高達90%以上，已達國際最高標準(85~90%)，表示捕碳劑經過60-150小時仍所具有極高之穩定性，且明顯高於CaO、CaCO3、Limestone、Li4SiO4等材料。 The international dry CO 2 capture agent is suitable for different temperature ranges, and it is most common to contain CaO, alkaline minerals and lithium niobate at temperatures above 600 °C. As shown in Figure 9, the Ca:Al=7:1 carbon-trapping agent particles, powder and CaO, CaCO 3 , Limestone, Li 4 SiO 4 and other materials are adsorbed/desorbed by TGA at 650-750 °C. 2 to 40 circuit (60 hours) performance comparison. The results showed that: (1) In the 40-circuit test, the carbon-trapping amount of the carbon-trapping agent of the present invention was maintained at 50-55 wt%, and the stability was at least 95-98%. As shown in Figure 10, even in 100 loop tests, it is still as high as 90%. (2) CaO has a high carbon capture capacity due to its purity of 95-99%, but the 40-cycle stability is about 85-90%, and it shows a continuous decline trend. (3) The carbon capture capacity of materials such as Limestone and Li 4 SiO 4 is about 25-45%, and the 40-time loop stability is about 80%. (4) In this test, CaCO 3 has poor stability, and its initial carbon capture amount is about 65 wt%, which is 40-45 wt% after only 5-10 loops, and the stability is about 60-70% of the original carbon capture. The carbon capture agent of the invention has a loop stability of more than 90% through 40-100 cycles, and has reached the international highest standard (85-90%), indicating that the carbon capture agent has extremely high stability after 60-150 hours, and It is obviously higher than CaO, CaCO 3 , Limestone, Li 4 SiO 4 and other materials.
如此，可藉由本發明達到至少下列優點： Thus, at least the following advantages can be achieved by the present invention:
(1)可調整Ca：Al比例至少1~30倍等優點，並能獲得批次公斤級以上產量之CO2捕獲劑。 (1) It can adjust the ratio of Ca:Al to at least 1~30 times, and can obtain CO 2 capture agent with a batch output of more than kilograms.
(2)可操作於400~800℃溫度範圍吸收二氧化碳。 (2) It can operate to absorb carbon dioxide in the temperature range of 400~800 °C.
(3)捕碳量隨較高Ca：Al比例而增加，初始捕碳量可達10~70wt%(gCO2/g sorbent)， (3) The amount of carbon capture increases with the higher ratio of Ca:Al, and the initial carbon capture can reach 10~70wt% (gCO 2 /g sorbent).
(4)高溫>750℃條件仍可適用，CO2濃度範圍廣泛達5-100%(v/v)， (4) The conditions of high temperature >750 °C are still applicable, and the range of CO 2 concentration is 5-100% (v/v).
(5)750℃之捕碳/除碳迴圈可維持長時間穩定性90%至少達150小時。 (5) The carbon capture/carbon removal loop at 750 °C maintains long-term stability of 90% for at least 150 hours.
綜上所述，本發明利用工程方法與裝置可批次製造公斤級產量之 捕碳劑，具有降低製造成本之潛能，並能應用於相關固定式或是流動式等反應器中，進行中高溫CO2捕獲研究。其重要性質包含：可改變Ca：Al比例達1-30倍、具有10-65wt%起始捕碳量、經過40-100次迴路(60-150小時)穩定性高達90%以上。此外，本發明捕碳劑Ca-Al-CO3係利用層狀無機結構做為模板製造具有創新特性，在國際間如何利用工程製造方法與裝置生產此系列材料，並應用在600℃以上捕捉CO2尚無相關報導。本發明可有效改善習用之種種缺點，進而使本發明之產生能更進步、更實用、更符合使用者之所須，確已符合發明專利申請之要件，爰依法提出專利申請 In summary, the invention can utilize the engineering method and the device to batch-produce the carbon-trapping agent of the kilo-scale production, has the potential of reducing the manufacturing cost, and can be applied to the related fixed or flow type reactors for the medium and high temperature. CO 2 capture study. Its important properties include: the ratio of Ca:Al can be changed by 1-30 times, the initial carbon capture amount is 10-65wt%, and the stability is over 90% after 40-100 loops (60-150 hours). In addition, the carbon-trapping agent Ca-Al-CO 3 of the present invention utilizes a layered inorganic structure as a template to manufacture innovative characteristics, how to use the engineering manufacturing method and device to produce this series of materials internationally, and to apply CO above 600 ° C to capture CO 2 There are no relevant reports. The invention can effectively improve various disadvantages of the conventional use, thereby making the invention more progressive, more practical and more suitable for the user, and indeed meets the requirements of the invention patent application, and submits a patent application according to law.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍；故，凡依本發明申請專利範圍及發明說明書內容所作之簡單的等效變化與修飾，皆應仍屬本發明專利涵蓋之範圍內。 However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto; therefore, the simple equivalent changes and modifications made in accordance with the scope of the present invention and the contents of the invention are modified. All should remain within the scope of the invention patent.
1‧‧‧混合 1‧‧‧mix
2‧‧‧固液分離 2‧‧‧Solid-liquid separation
3‧‧‧乾燥與擠壓 3‧‧‧Drying and extrusion
4‧‧‧粉碎與輸送 4‧‧‧Smashing and conveying
5‧‧‧煅燒成型 5‧‧‧ calcination
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