201208768 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種提升漿態床反應器產率之方法，尤指 涉及一種在漿態床反應器（SlurryReactor)中利用吸收劑移除 反應中之部份產物或副反應之反應物，特別係指可提昇可逆反 應之反應物轉化率及主產物之選擇率之方法者。 【先前技術】 漿態床反應器因液體溶劑熱容大、熱傳好且設備簡單，可 適於放熱性反應產品如合成氣合成甲醇、二甲越等之工業生 產，舉列而言，曱醇在2009年全世界總產能約5〇〇〇萬嘲，其 經濟市場相當大，顯示漿態床反應器具備有可供發展之經濟性 效益。 一般而言，當化學反應屬於可逆反應時，反應最後會達到 熱力學平衡，而反應物之平衡轉化率係其可達之最高轉化率， 就工業生產來說，因為反應物無法完全利用，需要將產物中之 反應物分離循環再利用。在平衡轉化率越低下，需要循環之反 應物就越多，相對地，亦將會提高生產成本，若能將部分產物 移除，則可迫使化學平衡向產物端傾斜，以提高反應物之轉化 率。例如一氧化碳（C0)與二氧化氮（N〇2)反應生成二氧 化碳（C02)與一氧化氮（NO)之反應即屬於可逆反應，其 化學反應式如下： CO+N〇2^C02+NO ; 其平衡常數 Keq=[C02]eq[NO]eq/[CO]eq[N〇2]eq ’ 若能將反應 後之二氧化碳移除，則為了保持平衡常數定值’反應勢必將朝 201208768 右移動’如此將有更多之-氧化碳反應產生二氧化碳，進 提昇反應物之利用率。 或者，整個反應系統不只-條反應式，若為複雜反應，复 化學反應式如下： 〃201208768 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for increasing the yield of a slurry bed reactor, and more particularly to an absorbent removal reaction in a slurry bed reactor (Slurry Reactor) The reactants of some of the products or side reactions, in particular, are those which increase the conversion rate of the reactants of the reversible reaction and the selectivity of the main product. [Prior Art] The slurry bed reactor is suitable for industrial production of exothermic reaction products such as syngas synthesis methanol, dimethine, etc. due to its large heat capacity, good heat transfer and simple equipment. Alcohol has a total production capacity of about 50,000 in the world in 2009, and its economic market is quite large, indicating that the slurry bed reactor has economic benefits for development. In general, when a chemical reaction is a reversible reaction, the reaction will eventually reach a thermodynamic equilibrium, and the equilibrium conversion of the reactants is the highest conversion rate that can be achieved. For industrial production, because the reactants cannot be fully utilized, it is necessary to The reactants in the product are separated and recycled. The lower the equilibrium conversion rate, the more reactants need to be recycled. Relatively, the production cost will also increase. If part of the product can be removed, the chemical equilibrium can be forced to tilt toward the product end to improve the conversion of the reactants. rate. For example, the reaction of carbon monoxide (C0) with nitrogen dioxide (N〇2) to form carbon dioxide (C02) and nitric oxide (NO) is a reversible reaction, and its chemical reaction formula is as follows: CO+N〇2^C02+NO; Its equilibrium constant Keq=[C02]eq[NO]eq/[CO]eq[N〇2]eq ' If the carbon dioxide after the reaction can be removed, in order to maintain the equilibrium constant value, the reaction will move to the right of 201208768. 'There will be more - carbon oxides react to produce carbon dioxide, which increases the utilization of the reactants. Alternatively, the entire reaction system is not limited to a single reaction type. If it is a complex reaction, the complex chemical reaction formula is as follows:
(1) A + B = C + D(1) A + B = C + D
(2) A + D = E + F 如果上述c係主要產物’若能在反應過程巾移除D，則可 減少第(2)式之副產物生成，並可提高主產物c之選擇率。 ^ 纟文獻上即有一些利用此原理之例子，例如以固定床反應 器利用二氧化碳與氫氣生產曱醇時 (C〇2+H2eCH3〇H+H2〇) ’利用薄膜移除曱醇或水，可以提 高轉化率(Gallued and Basile，Im. L Hydrogen Engery，32, 5050, 2007)。惟，目前在文獻檢索上並無尋得任何移除漿態床之產 物以提昇反應物轉化率之探討。故，一般習用者係無法符合使 用者於實際使用時之所需。 • 【發明内容】 本發明之主要目的係在於，克服習知技藝所遭遇之上述問 題並提供一種移除漿態床反應器反應中之部份產物或副反應 之反應物，可提昇可逆反應之反應物轉化率及主產物之選擇 率，以增進漿態床反應器之生產性，達到有助於工業化生產而 具備經濟效益之方法者。 為達以上之目的，本發明係一種提升漿態床反應器產率之 方法’係建立具有再生裝置或置換裝置之漿態床反應器；在該 漿態床反應器尹加入吸收劑，其中該吸收劑係為可與產物或副 4 201208768 反應之反應物結合之物質；以及將結合產物或反應物之吸收劑 輪送至該再生裝置，經由該再生裝置再生後重複使用以維持該 漿態床反應器中吸收劑之吸收性能；或將結合產物或反應物之 吸收劑輸送至該置換裝置，經由該置換裝置不斷移除舊之吸收 劑並加入新之吸收劑以維持該漿態床反應器中吸收劑之吸收 性能。 【實施方式】 • 請參閱『第1圖』所示，係本發明之漿態床反應器與吸收 劑及其再生或置換裝置之示意圖。如圖所示：本發明係一種提 升漿態床反應器產率之方法，係移除漿態床反應器（slurry Reactor)反應中之部份產物或副反應之反應物，可提昇可逆反 應之反應物轉化率及主產物之選擇率’以增進漿態床反應器之 生產性’進而有助於工業化生產者，其至少包含下列步驟： (A) 建立具有再生裝置11或置換裝置12之漿態床反 應器1 ’且該再生裝置11或置換裝置12係可安裝於該漿態 • 床反應器1内部或外部； (B) 在該漿態床反應器1中加入吸收劑2，其中該吸收 劑2係為可與產物或副反應之反應物結合之物質，並可為液體 或固體；以及 (C) 將結合產物或反應物之吸收劑2輸送至該再生裝置 1 1，經由該再生裝置11再生後重複使用以維持該漿態床反 應器1中吸收劑之吸收性能；或 (D) 將結合產物或反應物之吸收劑2輸送至該置換裝置 1 2’經由該置換裝置12不斷移除舊之吸收劑並加入新之吸 201208768 收劑以維持該漿態床反應器1中吸收劑之吸收性能。 當本發明於運用時，在漿態床反應器1中除了溶劑及觸媒 外，另加入可與產物或副反應之反應物結合之吸收劑2，使其 結合後降低反應器1中產物之濃度，使反應依勒沙特列原理朝 向產物端移動，以提高反應物之轉化率；也可與副反應之反應 物結合，以減少副反應發生之量，進而提昇主產物之選擇率。 繼之’可將此結合某些產物或反應物之吸收劑2輸送至再生裝 置11移除吸收物質後，再送回該漿態床反應器1中重複使 用’亦或係將此吸收後之吸收劑經由置換裝置12移除並加入 新吸收劑至該漿態床反應器1中更新使用。 請參閱『第2 A圖及第2 B圖』所示，係分別為本發明未 移除水分對二曱醚產量之影響示意圖、及本發明移除水分對二 甲醚產量之影響示意圖。如圖所示··本發明於一較佳實施例 中’係以吸收劑移除反應中部分產物為例。在合成氣 (CO/C〇2/H2) —步法生產二曱醚之漿態床反應器中，其化學 反應可以下列三式表示： (1) C〇+2H2^CH3OH ； (2) 2CH3OH㈠CH30CH3+H20 ; ⑶ co+h2o㈠co2+h2 ; 其中一甲越係主要產物，當加入吸收劑，水分被吸收後將 可使上述第(2)式之二甲酸產量增加’亦可使上述第(3)式之二 氧化碳產量變少以提高二甲醚之選擇率。如第2 A圖及第2 B 圖所示，其係以一維柱狀流模擬CO/C〇2/H2/N2=29/3/62/4之合 成氣’在無水分移除所得到產物中水、二氧化碳及二甲醚之濃 度曲線3a、4a及5a ’以及有水分移除所得到產物中水、二 201208768 氧化碳及二曱醚之濃度曲線3b、4b及5b之變化顯示中，可 見本實施例二甲醚分率約提昇20% ;由此可知，水分之移除將 有助於二曱醚分率之提昇。於其中，本實施例使用之吸收劑係 為世界專利第WO 85/00875號提及之高溫吸水脫水劑 KN〇3/LiN〇2 ’且該吸收劑係可經再生裝置移除水分後重複利 用’或經置換裝置移除後更新利用。 本發明於另一較佳實施例中，係以吸收劑移除反應中副反 應之反應物為例。在二氧化碳與氫氣生產曱醇之漿態床反應器 中，其化學反應式如下： C〇2+3H2^CH3OH+H20 ； 在加入沸石等吸收劑後，係可將水分固定在吸收劑中，利 用降低反應器中水之分率，使二氧化碳轉化率提高，進而增加 曱醇之產量。其中吸水後之沸石係可循環至漿態床反應器外之 再生裝置移除水分後重複利用，或經置換裝置移除後更新利 用0 綜上所述，本發明係一種提升漿態床反應器產率之方法， 可有效改善習用之種種缺點’係在漿態床反應器（Sluny Reactor)中利用吸收劑移除反應中之部份產物或副反應之反應 物，可提昇可逆反應之反應物轉化率及主產物之選擇率，以增 進漿態床反應器之生產性’達到有助於工業化生產而具備經濟 效益者，進而使本發明之産生能更進步、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。 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[S] 7 201208768 明說明書内容所作之簡單的等效變化與修飾，皆應仍屬本發明 專利涵蓋之範圍内。 【圖式簡單說明】 第1圖，係本發明之装態床反應器與吸收劑及其再生或置換 裝置之示意圖。 第2 A圖’係本發明未移除水分對二帽產量之影響示意圖。 第2 B圖’係本發明移除水分對二甲喊量之影響示意圖。 • 【主要元件符號說明】 ~ 漿態床反應器1 再生裝置11 置換裝置12 吸收劑2 濃度曲線3a、4a及5a 濃度曲線3b、4b及5b(2) A + D = E + F If the above-mentioned c-based main product ' can remove D in the reaction process, the by-product formation of the formula (2) can be reduced, and the selectivity of the main product c can be improved. ^ There are some examples of the use of this principle in the literature, such as the use of carbon dioxide and hydrogen to produce sterols in a fixed-bed reactor (C〇2+H2eCH3〇H+H2〇), using a film to remove sterols or water, Increase conversion (Gallued and Basile, Im. L Hydrogen Engery, 32, 5050, 2007). However, there is currently no search for literature to remove the product of the slurry bed to increase the conversion rate of the reactants. Therefore, the general practitioner cannot meet the needs of the user in actual use. • SUMMARY OF THE INVENTION The primary object of the present invention is to overcome the above problems encountered in the prior art and to provide a reactant for removing some of the products or side reactions in the slurry bed reactor reaction, thereby enhancing the reversible reaction. The reactant conversion rate and the selectivity of the main product are used to improve the productivity of the slurry bed reactor, and to achieve economical benefits for industrial production. For the above purposes, the present invention is a method for increasing the yield of a slurry bed reactor by establishing a slurry bed reactor having a regeneration device or a displacement device; wherein the slurry bed reactor is added with an absorbent, wherein The absorbent is a substance that can be combined with the product or the reactant of the reaction of the group 4 201208768; and the absorbent of the combined product or reactant is transferred to the regeneration device, and is reused after being regenerated by the regeneration device to maintain the slurry bed. The absorbent property of the absorbent in the reactor; or the absorbent of the combined product or reactant is delivered to the displacement device, the old absorbent is continuously removed via the displacement device and a new absorbent is added to maintain the slurry bed reactor The absorption properties of the medium absorbent. [Embodiment] FIG. 1 is a schematic view showing a slurry bed reactor and an absorbent and a regenerating or replacing device thereof according to the present invention. As shown in the figure: the present invention is a method for increasing the yield of a slurry bed reactor, which is to remove some of the products in the slurry reactor reaction or the side reaction reactants, thereby improving the reversible reaction. The conversion of the reactants and the selectivity of the main product 'to improve the productivity of the slurry bed reactor' and thus to the industrial producers, comprising at least the following steps: (A) establishing a slurry having a regeneration device 11 or a displacement device 12 a bed reactor 1' and the regeneration device 11 or the displacement device 12 may be installed inside or outside the slurry bed reactor 1; (B) adding an absorbent 2 to the slurry bed reactor 1, wherein The absorbent 2 is a substance which can be combined with a product or a side reaction reactant, and can be a liquid or a solid; and (C) a combined product or reactant absorbent 2 is supplied to the regeneration device 1 via the regeneration. The device 11 is reused after regeneration to maintain the absorption performance of the absorbent in the slurry bed reactor 1; or (D) the absorbent product 2 of the combined product or reactant is delivered to the displacement device 1 2' via the replacement device 12 Remove old absorbent A new suction 201208768 is added to maintain the absorption properties of the absorbent in the slurry bed reactor 1. When the present invention is applied, in addition to the solvent and the catalyst, the slurry reactor 1 is further added with an absorbent 2 which can be combined with the product or the side reaction reactant, and combined to reduce the product in the reactor 1. The concentration shifts the reaction to the product end to increase the conversion rate of the reactants; it can also be combined with the side reaction reactants to reduce the amount of side reactions, thereby increasing the selectivity of the main product. Following this, the absorbent 2 combined with certain products or reactants can be sent to the regeneration device 11 to remove the absorbent material, and then sent back to the slurry bed reactor 1 for repeated use or the absorption after absorption. The agent is removed via the displacement device 12 and a new absorbent is added to the slurry bed reactor 1 for renewed use. Please refer to "Fig. 2A and Fig. 2B" for the effect of the unremoved moisture on the yield of dioxane in the present invention, and the effect of the removal of moisture on the yield of dimethyl ether of the present invention. As shown in the drawings, the present invention is exemplified by a part of the product in the absorbent removal reaction in a preferred embodiment. In a slurry gas reactor in which syngas (CO/C〇2/H2) is produced in a step-by-step process, the chemical reaction can be represented by the following three formulas: (1) C〇+2H2^CH3OH; (2) 2CH3OH(1)CH30CH3 +H20 ; (3) co+h2o(1)co2+h2; one of the major products of the methine group, when added to the absorbent, the water will be absorbed to increase the yield of the dicarboxylic acid of the above formula (2)' The carbon dioxide production of the formula is reduced to increase the selectivity of dimethyl ether. As shown in Fig. 2A and Fig. 2B, it is a one-dimensional column flow simulation of CO/C〇2/H2/N2=29/3/62/4 syngas' obtained without moisture removal. The changes in the concentration curves 3a, 4a and 5a' of water, carbon dioxide and dimethyl ether in the product, and the concentration curves 3b, 4b and 5b of water in the product obtained by moisture removal, 2201208768 carbon oxide and dioxime are shown. It can be seen that the dimethyl ether fraction of the present embodiment is increased by about 20%; thus, it can be seen that the removal of moisture will contribute to the improvement of the diterpene ether fraction. The absorbent used in the present embodiment is the high-temperature water-absorbing dehydrating agent KN〇3/LiN〇2′ mentioned in the patent WO 85/00875, and the absorbent can be reused after removing moisture by the regeneration device. 'Or update the use after the replacement device is removed. In another preferred embodiment of the invention, the reactant of the side reaction in the absorbent removal reaction is exemplified. In the slurry-bed reactor of carbon dioxide and hydrogen to produce sterol, the chemical reaction formula is as follows: C〇2+3H2^CH3OH+H20; After adding an absorbent such as zeolite, the moisture can be fixed in the absorbent, and utilized. Reduce the water fraction in the reactor, increase the carbon dioxide conversion rate, and increase the yield of sterol. The zeolite after water absorption can be recycled to the regeneration device outside the slurry bed reactor to remove water, reused, or replaced by a replacement device. The invention is a lift slurry bed reactor. The method of yield can effectively improve the disadvantages of the conventional use. In the slurry bed reactor (Sluny Reactor), the absorbent removes some of the products in the reaction or the side reaction reactants, and the reactants for the reversible reaction can be enhanced. The conversion rate and the selectivity of the main product to improve the productivity of the slurry bed reactor to achieve economic benefits for industrial production, thereby making the invention more progressive, more practical, and more user-friendly. It is necessary to 'have met the requirements of the invention patent application and file a patent application according to law. However, the above description is only for the preferred embodiment of the present invention, and the scope of the present invention cannot be limited thereto; therefore, the scope of the patent application and the content of the specification [S] 7 201208768 are simple. Equivalent variations and modifications are still within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the assembled bed reactor and absorbent of the present invention and its regeneration or replacement device. Fig. 2A is a schematic view showing the effect of the unremoved moisture of the present invention on the yield of the two caps. Fig. 2B is a schematic view showing the effect of removing moisture on the amount of dimethyl shark in the present invention. • [Main component symbol description] ~ Slurry bed reactor 1 Regeneration device 11 Displacement device 12 Absorbent 2 Concentration curves 3a, 4a and 5a Concentration curves 3b, 4b and 5b