TWI466824B - Method for reusing deactivated absorbent of carbon dioxide capture system and method for sequestrating carbon dioxide - Google Patents
Method for reusing deactivated absorbent of carbon dioxide capture system and method for sequestrating carbon dioxide Download PDFInfo
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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
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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
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Description
本發明係有關於一種失活吸附劑再利用及封存CO2 的方法，且特別是有關於一種捕獲CO2 系統之失活吸附劑再利用及封存CO2 的方法。The present invention relates to a deactivation of the adsorbent and the method of recycling of CO 2 sequestration, and more particularly relates to an inactivated CO 2 capture systems and methods for recycling the adsorbent of CO 2 sequestration.
為了減緩全球暖化的速度，以維護人類的生存環境，世界各國致力於降低CO2 的排放量，為此，一種捕獲CO2 系統被提出。In order to slow down the global warming and maintain the living environment of human beings, countries around the world are working to reduce CO 2 emissions. To this end, a CO 2 capture system has been proposed.
習知的捕獲CO2 系統係利用一吸附劑(例如氧化鈣)在適當的溫度下吸附CO2 ，當吸附劑使用一段時間後，可利用煅燒(calcine)方式將其再生。然而，氧化鈣經過多次煅燒後，氧化鈣表面被碳酸鈣所包覆，並無法再藉由煅燒方式使其再生，只好將失活吸附劑排放，以維持系統捕獲CO2 的效率。Conventional capture CO 2 systems utilize a sorbent (e.g., calcium oxide) to adsorb CO 2 at a suitable temperature, and when the adsorbent is used for a period of time, it can be regenerated using a calcine. However, after the calcium oxide is calcined several times, the surface of the calcium oxide is coated with calcium carbonate, and can no longer be regenerated by calcination, so that the deactivated adsorbent is discharged to maintain the efficiency of the system for capturing CO 2 .
此外，捕獲CO2 系統會排放出高濃度的二氧化碳，高濃度的CO2 必須透過特定的方式進行封存(storage)，以減少CO2 排放量。目前的CO2 封存方法包括地質封存(geologic sequestration)、礦化封存(mineral carbonation)或海洋封存(ocean storage)，然而，上述方法操作成本高且可能對生態造成不利的影響。In addition, the capture CO 2 system emits a high concentration of carbon dioxide, and high concentrations of CO 2 must be stored in a specific manner to reduce CO 2 emissions. Current CO 2 sequestration methods include geologic sequestration, mineral carbonation, or ocean storage. However, the above methods are costly to operate and may have adverse ecological impacts.
因此，本發明提供一種捕獲CO2 系統之失活吸附劑再利用及封存CO2 的方法，以解決上述問題。Accordingly, the present invention provides a method of capturing the deactivated adsorbent of a CO 2 system for reuse and sequestration of CO 2 to solve the above problems.
本發明提供一種捕獲CO2 系統之失活吸附劑再利用的方法，包括以下步驟：提供一失活吸附劑，其中該失活吸附劑來自於一捕獲CO2 系統；以及將該失活吸附劑、CO2 、與水送至一第一反應槽中，以得到一碳酸鹽。The present invention provides a method of capturing a deactivated adsorbent reuse of a CO 2 system, comprising the steps of: providing an inactivated adsorbent, wherein the deactivated adsorbent is derived from a capture CO 2 system; and the deactivated adsorbent , CO 2 , and water are sent to a first reaction tank to obtain a monocarbonate.
本發明亦提供一種封存CO2 的方法，包括以下步驟：將一CO2 導入一水槽中，以得到一碳酸水溶液；以及將該碳酸水溶液與一失活吸附劑導入一第二反應槽，以達到封存CO2 的效果。The invention also provides a method for sequestering CO 2 , comprising the steps of: introducing a CO 2 into a water tank to obtain an aqueous solution of carbonic acid; and introducing the aqueous solution of carbonic acid and a deactivated adsorbent into a second reaction tank to achieve Seal the effect of CO 2 .
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳細說明如下：The above and other objects, features and advantages of the present invention will become more <RTIgt;
請參見第1圖，本發明提供一種捕獲CO2 系統之失活吸附劑再利用的裝置100，此裝置100包括捕獲CO2 系統120、注水管130、CO2 供應器140、第一反應槽150，其中捕獲CO2 系統120提供失活吸附劑122，注水管130提供水132，而CO2 供應器140提供CO2 ，因此，第一反應槽150中會存在失活吸附劑122、水132與CO2 142。Referring to FIG. 1 , the present invention provides an apparatus 100 for capturing deactivated adsorbent reuse of a CO 2 system. The apparatus 100 includes a capture CO 2 system 120, a water injection pipe 130, a CO 2 supply 140, and a first reaction tank 150. Wherein the capture CO 2 system 120 provides a deactivated adsorbent 122, the water injection pipe 130 provides water 132, and the CO 2 supply 140 provides CO 2 , thus, the deactivated adsorbent 122, water 132 and the first reaction tank 150 may be present CO 2 142.
上述失活吸附劑122包括金屬氧化物與碳酸金屬化合物，且金屬氧化物與碳酸金屬化合物之比例為約(70%-50%)：(30%-50%)。The above deactivated adsorbent 122 comprises a metal oxide and a metal carbonate compound, and the ratio of the metal oxide to the metal carbonate compound is about (70%-50%): (30%-50%).
金屬氧化物包括氧化鈣(CaO)、氧化鋅(ZnO)、氧化鎂(MgO)、氧化錳(MnO2 )、氧化鎳(NiO)或氧化鉛(PbO)，而碳酸金屬化合物包括碳酸鈣(CaCO3 )、碳酸鋅(ZnCO3 )、碳酸鎂(MgCO3 )、碳酸錳(Mn(CO3 )2 )、碳酸鎳(NiCO3 )或碳酸鉛(PbCO3 )。The metal oxide includes calcium oxide (CaO), zinc oxide (ZnO), magnesium oxide (MgO), manganese oxide (MnO 2 ), nickel oxide (NiO) or lead oxide (PbO), and the metal carbonate compound includes calcium carbonate (CaCO). 3 ), zinc carbonate (ZnCO 3 ), magnesium carbonate (MgCO 3 ), manganese carbonate (Mn(CO 3 ) 2 ), nickel carbonate (NiCO 3 ) or lead carbonate (PbCO 3 ).
上述之CO2 142來自捕獲CO2 系統所捕獲之CO2 ，或者是來自捕獲CO2 系統中之一煙道氣中尚未被捕獲之CO2 。The above CO 2 from the CO 2 142 CO 2 capture system captures the, or CO 2 capture from gas system of one of the flue Not captured CO 2.
當失活吸附劑122與水132、CO2 142進行反應時，會得到碳酸金屬化合物，此產物可以再度回收作為吸附劑，或者可應用於相關行業，例如水泥業或造紙業。When the deactivated adsorbent 122 is reacted with water 132, CO 2 142, a metal carbonate compound is obtained, which can be recycled again as an adsorbent, or can be applied to related industries such as the cement industry or the paper industry.
於一實施例中，失活吸附劑之組成為碳酸鈣40%與氧化鈣60%，當水與失活吸附劑反應時，會得到碳酸氫鈣(Ca(OH)2 )水溶液(如反應式(1))，再通入CO2 ，會得到碳酸鈣(CaCO3 )沉澱(如反應式(2))，反應式(1)、(2)如下：CaO+CaCO3 +H2 O→Ca(OH)2 -----(1)Ca(OH)2 +CO2 →CaCO3 +H2 O----(2)反應式(2)所得到之碳酸鈣之沉降體積(2.4-2.8 ml/g)大於原本碳酸鈣(1.1-1.4 ml/g)(或稱「重質碳酸鈣」)的沉降體積，因此，又可稱為「輕質碳酸鈣」。In one embodiment, the composition of the deactivated adsorbent is 40% calcium carbonate and 60% calcium oxide. When water reacts with the deactivated adsorbent, an aqueous solution of calcium hydrogencarbonate (Ca(OH) 2 ) is obtained (eg, a reaction formula). (1)), and then pass CO 2 to obtain calcium carbonate (CaCO 3 ) precipitation (such as reaction formula (2)), and the reaction formulas (1) and (2) are as follows: CaO+CaCO 3 +H 2 O→Ca (OH) 2 -----(1)Ca(OH) 2 +CO 2 →CaCO 3 +H 2 O---(2) The sedimentation volume of calcium carbonate obtained by the reaction formula (2) (2.4- 2.8 ml/g) is larger than the sedimentation volume of the original calcium carbonate (1.1-1.4 ml/g) (or "heavy calcium carbonate"), so it can also be called "light calcium carbonate".
此外，本發明提供一種捕獲CO2 系統之失活吸附劑再利用的方法，包括以下步驟，首先提供失活吸附劑，其中失活吸附劑來自於捕獲CO2 系統。之後，將將失活吸附劑、水、CO2 通入第一反應槽中，以得到碳酸金屬化合物。Further, the present invention provides a method of inactivating CO 2 adsorbent systems reuse capture, comprising the steps of, first providing deactivated adsorbent, wherein the sorbent deactivation from CO 2 capture system. Thereafter, the deactivated adsorbent, water, and CO 2 are introduced into the first reaction tank to obtain a metal carbonate compound.
須注意的是，藉由本發明所提供之裝置與方法，可使失活吸附劑再利用，提高失活吸附劑之利用價值，且以另一角度來看，此方法亦會消耗CO2 ，亦可稱為封存CO2 的方法。It should be noted that by using the apparatus and method provided by the present invention, the deactivated adsorbent can be reused to increase the utilization value of the deactivated adsorbent, and from another point of view, the method also consumes CO 2 . It can be called a method of sequestering CO 2 .
再者，本發明另提供一種封存CO2 的裝置200，請參見第2圖，第2圖中標號與第1圖相同者，代表相同元件。封存CO2 的裝置200包括捕獲CO2 系統120、水槽210與第二反應槽220，其中捕獲CO2 系統120提供CO2 124溶解於水槽210中，以得到碳酸水溶液212，之後，捕獲CO2 系統120所提供失活吸附劑122與碳酸水溶液212於第二反應槽220中進行反應，反應後會得到低濃度的CO2 222與混合溶液224，其中混合溶液224包括金屬離子、含碳離子與含碳礦物。Furthermore, the present invention further provides a device 200 for storing CO 2 . Referring to FIG. 2 , the same reference numerals as in FIG. 1 denote the same elements. The apparatus 200 for sequestering CO 2 includes a capture CO 2 system 120, a water tank 210 and a second reaction tank 220, wherein the capture CO 2 system 120 provides CO 2 124 dissolved in the water tank 210 to obtain an aqueous carbonate solution 212, after which the CO 2 system is captured. The deactivated adsorbent 122 and the aqueous solution 212 are reacted in the second reaction tank 220 to obtain a low concentration of CO 2 222 and a mixed solution 224, wherein the mixed solution 224 includes metal ions, carbon ions and Carbon minerals.
上述失活吸附劑122之種類同上所述，在此不再贅述。The types of the above-mentioned deactivated adsorbents 122 are the same as those described above, and will not be described herein.
上述之CO2 124來自捕獲CO2 系統120所捕獲之CO2 ，或者是來自捕獲CO2 系統120中之一煙道氣中尚未被捕獲之CO2 。此外，上述之CO2 124來自其它CO2 來源。The above CO 2 124 from the CO 2 capture system to capture the 120 CO 2, or in the gas flue Not one of the captured CO from the CO 2 capture system 1202. In addition, the CO 2 124 described above is derived from other sources of CO 2 .
本發明提供之封存CO2 的方法，包括以下步驟，先將CO2 124導入水槽210中，以得到碳酸水溶液212，之後再將碳酸水溶液212與失活吸附劑122導入第二反應槽220中進行反應，以達到封存CO2 的效果。The method for storing CO 2 provided by the present invention comprises the steps of: introducing CO 2 124 into the water tank 210 to obtain the aqueous solution 212, and then introducing the aqueous solution 212 and the deactivated adsorbent 122 into the second reaction tank 220. The reaction is carried out to achieve the effect of sequestering CO 2 .
當CO2 溶解於水中時，會進行下述化學式(3)-(5)的反應：When CO 2 is dissolved in water, the reactions of the following chemical formulas (3) to (5) are carried out:
當碳酸水溶液212與失活吸附劑122混合時，會發生CO2 溶解封存反應(化學式(6)-(8))與CO2 礦化封存反應(化學式(9)-(10))，具體反應式如下：CO2 溶解封存反應：When the aqueous carbonate solution 212 is mixed with the deactivated adsorbent 122, a CO 2 dissolution and sequestration reaction (chemical formulas (6) to (8)) and a CO 2 mineralization sequestration reaction (chemical formulas (9) to (10)) occur, and a specific reaction occurs. The formula is as follows: CO 2 dissolution storage reaction:
CO2 礦化封存反應：CO 2 mineralization and storage reaction:
其中M+a 為金屬陽離子，當失活吸附劑包括氧化鈣與碳酸鈣時，M+a 主要為Ca2+ ，以及其他微量陽離子，例如Mg2+ 、Fe2+ 、Fe3+ 等。Z-b 為系統中除了CO3 2- 以外的陰離子，例如HCO3 - 、SO4 2- 、Cl- 等。Wherein M + a is a metal cation, and when the deactivated adsorbent comprises calcium oxide and calcium carbonate, M + a is mainly Ca 2+ , and other trace cations such as Mg 2+ , Fe 2+ , Fe 3+ , and the like. Z- b is an anion other than CO 3 2- in the system, such as HCO 3 - , SO 4 2- , Cl - and the like.
於一實施例中，當失活吸附劑包括氧化鈣與碳酸鈣時(氧化鈣與水反應會形成氫氧化鈣)，溶解封存反應會得到鈣離子(Ca2+ )與碳酸氫根離子(HCO3 - )，而礦化封存反應會得到碳酸鈣(CaCO3 )。In one embodiment, when the deactivated adsorbent comprises calcium oxide and calcium carbonate (calcium oxide reacts with water to form calcium hydroxide), the dissolution and sequestration reaction results in calcium ions (Ca 2+ ) and bicarbonate ions (HCO). 3 - ), while the mineralization sequestration reaction will give calcium carbonate (CaCO 3 ).
此外，經過實驗模擬結果，相較於習知使用單純的碳酸鈣封存CO2 ，本發明使用失活吸附劑封存CO2 的方法可達到較佳的封存效果，具體實驗結果請參見實施例。In addition, after the experimental simulation results, compared with the conventional use of simple calcium carbonate to store CO 2 , the method for storing CO 2 by using the deactivated adsorbent can achieve better sealing effect. For the specific experimental results, please refer to the examples.
另外，請參見第3圖，此圖顯示捕獲CO2 系統之失活吸附劑再利用的裝置100與封存CO2 的裝置200兩者串聯的裝置300。第3圖中標號與第1-2圖相同者，代表相同符號，在此不再贅述。Also, see Figure 3, both the display device 300 of this FIG deactivation means CO 2 capture systems reuse the adsorbent and storage of CO 2 100 200 series. The same reference numerals are used in the third drawing to refer to the same reference numerals and will not be described again.
串聯裝置300先藉由第一反應槽150進行反應得到一混合物154，混合物154包括未反應之失活吸附劑或碳酸金屬化合物。之後，再將混合物154、水132與CO2 124送至第二反應槽220，進行CO2 封存反應，反應後會得到低濃度的CO2 222與混合溶液224，其中混合溶液224包括金屬離子、含碳離子與含碳礦物。The series unit 300 is first reacted by the first reaction tank 150 to obtain a mixture 154 comprising an unreacted deactivated adsorbent or a metal carbonate compound. Thereafter, the mixture 154, the water 132 and the CO 2 124 are sent to the second reaction tank 220 to perform a CO 2 sequestration reaction. After the reaction, a low concentration of CO 2 222 and a mixed solution 224 are obtained, wherein the mixed solution 224 includes metal ions, Carbon ions and carbonaceous minerals.
綜上所述，本發明提供捕獲CO2 系統之失活吸附劑再利用的方法，此方法能夠將失活吸附劑再利用，提高失活吸附劑之利用價值。此外，本發明亦提供封存CO2 的方法，此方法能夠將高濃度的CO2 轉變成含碳離子溶液與低濃度的CO2 ，以達到封存效果。In summary, the present invention provides a method for capturing the deactivated adsorbent of a CO 2 system, which can reuse the deactivated adsorbent and increase the utilization value of the deactivated adsorbent. In addition, the present invention also provides a method for sequestering CO 2 , which is capable of converting a high concentration of CO 2 into a carbon ion solution and a low concentration of CO 2 to achieve a sequestration effect.
【實施例】[Examples]
比較例1-4Comparative Example 1-4
比 較例1 與25℃ 1 Kg純水進行反應；比較例2 與25℃ 1 Kg海水進行反應；比較例3 與50℃ 1 Kg純水下進行反應；比較例4 與50℃ 1 Kg海水進行反應。比較例1-4 皆與0.2莫耳的碳酸鈣進行反應，反應結果請參見表1。For Comparative Example 1 1 Kg of pure water of 25 deg.] C the reaction; Comparative Example 2 is reacted with 1 Kg water 25 ℃; Comparative Example 3 is reacted with 1 Kg of pure water 50 ℃; Comparative Example 4 1 Kg water and 50 ℃ reaction. Comparative Examples 1-4 were all reacted with 0.2 mol of calcium carbonate. See Table 1 for the results of the reaction.
CTsys 代表系統平衡時液相與固相之CO2 總含量，Ini代表初始加入的CaCO3 ，因此，系統平衡時CO2 總封存量應為CTsys -Ini CaCO3 。C Tsys represents the total CO 2 content of the liquid phase and the solid phase in the system equilibrium, and Ini represents the CaCO 3 initially added. Therefore, the total CO 2 storage amount should be C Tsys -Ini CaCO 3 when the system is balanced.
由表1中比較例1-4可得知，單純的碳酸鈣、CO2 與水進行反應時，主要以溶解封存，沒有額外的礦化封存，且CO2 總封存量差不多。It can be seen from Comparative Examples 1-4 in Table 1 that when pure calcium carbonate and CO 2 are reacted with water, they are mainly stored by dissolution, without additional mineralization, and the total storage amount of CO 2 is about the same.
實施例1-4Examples 1-4
實施例1與25℃ 1 Kg純水進行反應；實施例2與25℃ 1 Kg海水進行反應；實施例3與50℃ 1 Kg純水進行反應；實施例4與25℃ 1 Kg純水進行反應。實施例1-4皆與0.2莫耳的碳酸鈣、0.2莫耳的氧化鈣與0.1莫耳的氫氧化鈣進行反應，反應結果請參見表2。Example 1 was reacted with 1 Kg of pure water at 25 ° C; Example 2 was reacted with 1 Kg of seawater at 25 ° C; Example 3 was reacted with 50 K of 1 Kg of pure water; and Example 4 was reacted with 25 ° C of 1 Kg of pure water. . Each of Examples 1-4 was reacted with 0.2 mol of calcium carbonate, 0.2 mol of calcium oxide and 0.1 mol of calcium hydroxide. The results of the reaction are shown in Table 2.
系統平衡時CO2 總礦化封存量為CTsys -IniCaCO3 -CTaq ，當數值大於0時，表示有CaCO3 沉澱；當數值小於0時，表示沒有額外的礦化封存。When the system balances, the total mineralized storage of CO 2 is C Tsys -IniCaCO 3 -C Taq . When the value is greater than 0, it indicates that there is CaCO 3 precipitation; when the value is less than 0, it means that there is no additional mineralization storage.
此外，由表1可得知單純的碳酸鈣、CO2 與水進行反應時，會以溶解封存為主，沒有額外的礦化封存。而比較例1-4與實施例1-4相比，由表1與表2的結果得知，比較例1-4沒有額外的礦化封存，而實施例1-4的礦化封存量較高，表示加入了氧化鈣與氫氧化鈣明顯的增加CO2 封存量。In addition, it can be seen from Table 1 that when pure calcium carbonate and CO 2 are reacted with water, they are mainly dissolved and sealed, and there is no additional mineralization. Comparing Comparative Examples 1-4 with Examples 1-4, it is known from the results of Tables 1 and 2 that Comparative Examples 1-4 have no additional mineralization sequestration, and the mineralization storage amounts of Examples 1-4 are higher. High means that the addition of calcium oxide and calcium hydroxide significantly increases the CO 2 storage.
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.
100．．．捕獲CO2 系統之失活吸附劑再利用的裝置100. . . Device for capturing deactivated adsorbent reuse of CO 2 system
120．．．捕獲CO2 系統120. . . Capture CO 2 system
122．．．失活吸附劑122. . . Inactivated adsorbent
124．．．CO2 124. . . CO 2
130．．．注水管130. . . Water injection pipe
132．．．水132. . . water
140．．．CO2 供應器140. . . CO 2 supply
142．．．CO2 142. . . CO 2
150．．．第一反應槽150. . . First reaction tank
152．．．碳酸金屬化合物152. . . Metal carbonate compound
154．．．混合物154. . . mixture
200．．．封存CO2 的裝置200. . . Device for storing CO 2
210．．．水槽210. . . sink
212．．．碳酸水溶液212. . . Aqueous carbonate solution
220．．．第二反應槽220. . . Second reaction tank
222．．．低濃度的CO2 222. . . Low concentration of CO 2
224．．．混合溶液224. . . mixture
300．．．捕獲CO2 系統之失活吸附劑再利用的裝置與封存CO2 的裝置的串聯裝置300. . . A tandem device for capturing a deactivated adsorbent reuse device of a CO 2 system and a device for storing CO 2
第1圖為一示意圖，用以說明本發明捕獲CO2 系統之失活吸附劑再利用的裝置。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the apparatus for recycling the deactivated adsorbent of the CO 2 system of the present invention.
第2圖為一示意圖，用以說明本發明封存CO2 的裝置。Figure 2 is a schematic view showing the apparatus for sequestering CO 2 of the present invention.
第3圖為一示意圖，用以說明串聯捕獲CO2 系統之失活吸附劑再利用的裝置與封存CO2 的裝置。Figure 3 is a schematic diagram showing the apparatus for reusing the deactivated adsorbent of the CO 2 system in series and the apparatus for sequestering CO 2 .
100．．．捕獲CO2 系統之失活吸附劑再利用的裝置100. . . Device for capturing deactivated adsorbent reuse of CO 2 system
120．．．捕獲CO2 系統120. . . Capture CO 2 system
122．．．失活吸附劑122. . . Inactivated adsorbent
130．．．注水管130. . . Water injection pipe
132．．．水132. . . water
140．．．CO2 供應器140. . . CO 2 supply
142．．．CO2 142. . . CO 2
150．．．第一反應槽150. . . First reaction tank
152．．．碳酸金屬化合物152. . . Metal carbonate compound
Claims (11)
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| TW100144779A TWI466824B (en) | 2011-12-06 | 2011-12-06 | Method for reusing deactivated absorbent of carbon dioxide capture system and method for sequestrating carbon dioxide |
| CN201110430353.1A CN103143256B (en) | 2011-12-06 | 2011-12-21 | Recycle of CO2Deactivated absorbent and sequestered CO of capture system2Method (2) |
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