本公示涉及一種羧化及氧化芳族化合物之整合方法。This disclosure relates to a method of integrating carboxylated and oxidized aromatic compounds.
鄰苯二甲酸和對苯二甲酸等芳族化合物是透過分別氧化鄰二甲苯和對二甲苯來製備。Aromatic compounds such as phthalic acid and terephthalic acid are prepared by separately oxidizing o-xylene and p-xylene.
另外，鄰苯二甲酸或對苯二甲酸也可以透過羧化甲苯得2-甲基苯甲酸或4-甲基苯甲酸，隨後氧化甲基團來製備。進行甲苯等芳族化合物之羧化能夠利用格利雅(Grignard)羧化和弗瑞德-克萊福特(Friedel-Crafts)羧化法。Alternatively, phthalic acid or terephthalic acid can also be prepared by carboxylating toluene to give 2-methylbenzoic acid or 4-methylbenzoic acid followed by oxidation of the methyl group. Carnation of an aromatic compound such as toluene can be carried out using Grignard carboxylation and Friedel-Crafts carboxylation.
專利US 3138626提出利用氯化鋁和二氧化碳來羧化甲苯。Patent US 3,138,626 teaches the use of aluminum chloride and carbon dioxide to carboxylate toluene.
US 7271286提出了一種方法，透過溫育來活化路易斯(Lewis)酸和CO2以產生芳族羧酸。No. 7,271,286 proposes a process for the activation of Lewis acid and CO2 by incubation to produce an aromatic carboxylic acid.
WO 2001/016072提出了一種方法，將芳族烴與K2CO3、Rb2CO3、Cs2CO3和Na2CO3等碳酸鹽進行反應，產生芳族羧酸及二元酸。WO 2001/016072 proposes a process for reacting an aromatic hydrocarbon with a carbonate such as K2 CO3 , Rb2 CO3 , Cs2 CO3 and Na2 CO3 to produce an aromatic carboxylic acid and a dibasic acid.
由Shlyakhtin等人撰寫的題為“在超臨界二氧化碳介質中羧化芳族化合物”一文提出在存在AlCl3、FeCl3、ZrCl4和ZnCl2等路易斯酸條件下，利用超臨界形態之二氧化碳來羧化芳族化合物。A paper entitled "Carboxylation of aromatic compounds in supercritical carbon dioxide medium" by Shlyakhtin et al. suggests the use of supercritical carbon dioxide to carboxylate in the presence of Lewis acids such as AlCl3 , FeCl3 , ZrCl4 and ZnCl2 . Aromatic compounds.
透過部份上述方法產生芳族單羧酸化合物，然後利用氧化劑來氧化存在其中的烷基團，產生芳族二羧酸。Producing an aromatic monocarboxylic acid compound by some of the above methods, and then using an oxidizing agent to oxygenThe alkyl group is present therein to produce an aromatic dicarboxylic acid.
因此，要從芳族烴中製備芳族二羧酸，本領域技術人員必須單獨採用兩種方法，即羧化及氧化。在此兩種方法中產生的流出物含有不同的催化劑及後來添加到流出物中的試劑，從而導致環境污染。Therefore, to prepare an aromatic dicarboxylic acid from an aromatic hydrocarbon, those skilled in the art must separately employ two methods, namely, carboxylation and oxidation. The effluent produced in both processes contains different catalysts and reagents that are later added to the effluent, resulting in environmental pollution.
而且，由此類方法製備的最終產品更可能含有因中間體不完全轉化而產生的雜質，因此需要進一步純化，從而增加生產成本。Moreover, the final product prepared by such methods is more likely to contain impurities resulting from incomplete conversion of the intermediate, and thus requires further purification, thereby increasing production costs.
因此，需要一種簡單高效的方法，能夠單步進行芳族化合物之羧化及氧化，使所有中間產物成為所要產品之轉化率最大。Therefore, there is a need for a simple and efficient method for single-step carboxylation and oxidation of aromatic compounds to maximize conversion of all intermediate products to desired products.
目的：purpose:
本公示的部份目的敍述如下：本公示之一個目的是，部份解決先有技術中的一個或多個問題，或至少提供一種有用的選擇。Some of the purposes of this disclosure are as follows: One purpose of this disclosure is to partially address one or more of the problems of the prior art, or at least provide a useful alternative.
本公示之另一個目的是，提供一種在一個連續步驟中羧化及氧化芳族化合物之整合方法。Another object of the present disclosure is to provide an integrated process for carboxylating and oxidizing aromatic compounds in a continuous step.
本公示之又一個目的是，提供一種簡單、生態友好和成本效益好的羧化及氧化芳族化合物之整合方法。Yet another object of the present disclosure is to provide a simple, eco-friendly and cost effective method of integrating carboxylated and oxidized aromatic compounds.
本公示之再一個目的是，提供一種純度最高和污染物最少的製備芳族二羧酸之整合方法。A further object of the present disclosure is to provide an integrated process for the preparation of aromatic dicarboxylic acids with the highest purity and minimal contaminants.
本公示還有一個目的，就是為羧化及氧化取代基芳族烴之整合方法提供一種試劑。It is also an object of the present disclosure to provide an agent for the integration of carboxylated and oxidized substituent aromatic hydrocarbons.
本公示再有一個目的，就是提供一種從苯中製備對苯二甲酸之整合方法。A further object of the present disclosure is to provide an integrated process for the preparation of terephthalic acid from benzene.
本公示之其他目的和優點從以下敍述中將變得更為明顯，但敍述本身無意限定本公示之範圍。Other objects and advantages of the present disclosure will become more apparent from the following description, but the description is not intended to limit the scope of the disclosure.
定義：definition:
在本公示上下文中的術語“連續步驟”是指單個步驟，其包括兩個分步驟，即在同一反應容器中相繼發生羧化及氧化反應。The term "continuous step" in the context of the present disclosure refers to a single step comprising two sub-steps, namely sequential carboxylation and oxidation reactions in the same reaction vessel.
亞臨界形態之CO2定義為同時具有液體和氣體性質之CO2。CO2 is defined as the critical aspect of alkylene having both nature of liquid and gaseous CO2.
甲苯甲酸包括鄰甲苯甲酸、間甲苯甲酸及對甲苯甲酸。Toluic acid includes o-toluic acid, m-toluic acid, and p-toluic acid.
二甲基苯甲酸包括從羧化二甲苯獲得的異構體產物。此類產物包括但不限於鄰二甲基苯甲酸、間二甲基苯甲酸及對二甲基苯甲酸。Dimethylbenzoic acid includes the isomer product obtained from carboxylated xylene. Such products include, but are not limited to, o-dimethylbenzoic acid, m-dimethylbenzoic acid, and p-dimethylbenzoic acid.
苯三酸包括但不限於1,2,3-苯三甲酸、1,2,4-苯三甲酸、1,3,4-苯三甲酸及1,3,5-苯三甲酸。Tricarboxylic acids include, but are not limited to, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,4-benzenetricarboxylic acid, and 1,3,5-benzenetricarboxylic acid.
概述：Overview:
本公示涉及一種在一個連續步驟中羧化及氧化具有至少一個烷基團取代基之芳族化合物之方法。用於羧化反應之催化劑在羧化反應過程中轉化成一種試劑，能夠原位氧化芳族化合物之烷基團。The present disclosure relates to a process for carboxylating and oxidizing an aromatic compound having at least one alkyl group substituent in one continuous step. The catalyst used in the carboxylation reaction is converted to a reagent during the carboxylation reaction to oxidize the alkyl group of the aromatic compoundin situ .
根據本公示之一個構想，提供了一種在一個連續步驟中羧化及氧化芳族化合物之方法。在先有技術中，附帶至少一個烷基團之芳族烴之羧化反應及附於芳族烴之烷基團之氧化反應各自單獨進行以獲得所要多元酸。透過此類傳統方法獲得的最終產品往往還要經過進一步的純化方法以脫除在不同的反應過程中捕集的中間產物。According to one aspect of the present disclosure, a method of carboxylating and oxidizing an aromatic compound in a continuous step is provided. In the prior art, the carboxylation reaction of an aromatic hydrocarbon with at least one alkyl group and the oxidation reaction of an alkyl group attached to an aromatic hydrocarbon are each carried out separately to obtain a desired polybasic acid. The final product obtained by such conventional methods is often subjected to further purification methods to remove intermediates captured during different reaction processes.
但是，在本公示之方法中，具有原位催化劑之芳環之羧化反應提供了一種試劑，能夠氧化附於芳環之烷基團。因此，兩種反應在同一反應容器中且在一個連續步驟中幾乎同時發生。因此，此方法稱為整合方法。However, in the presently disclosed method, the carboxylation reaction of the aromatic ring having thein situ catalyst provides an agent capable of oxidizing the alkyl group attached to the aromatic ring. Thus, both reactions occur in the same reaction vessel and occur almost simultaneously in one continuous step. Therefore, this method is called an integration method.
在本公示之方法中，在存在一種典型的催化劑條件下利用二氧化碳進行羧化，此催化劑在羧化過程中或羧化後轉化成一種試劑，或此催化劑能夠原位誘導氧化經羧化反應獲得的羧化烴上的烷基團。In the method of the present disclosure, carboxylation is carried out using carbon dioxide in the presence of a typical catalyst condition, and the catalyst is converted into a reagent during carboxylation or after carboxylation, or the catalyst is capable of inducing oxidation in the carboxylation reactionin situ . The alkyl group on the carboxylated hydrocarbon.
為說明起見，在一個連續步驟中發生的羧化反應和氧化反應在此圖示如下：
在上述反應中，因羧化反應形成之硝酸原位引發對甲苯甲酸之甲基團之氧化，產生對苯二甲酸。In the above reaction, the nitric acid formed by the carboxylation reaction initiates the oxidation of the methyl group of p-toluic acidin situ to produce terephthalic acid.
本發明方法：The method of the invention:
- 成本效益好，因為兩種不同的反應在同一容器中且在一個連續步驟中幾乎同時進行；及- 生態友好，因為流出物減少至少50%，透過耗盡所有中間產物及催化劑，達成芳族化合物成為芳族二羧酸之最佳轉化率。- Cost-effective because two different reactions are carried out in the same vessel and almost simultaneously in one continuous step; and - eco-friendly, because the effluent is reduced by at least 50%, by depleting all intermediates and catalysts, achieving aromatic The compound becomes the optimum conversion of the aromatic dicarboxylic acid.
本發明方法簡單，且以可接受之高產率和最少可能的中間產物雜質來獲得產品。The process of the invention is simple and the product is obtained in an acceptable high yield and with the least possible intermediate impurities.
進行羧化反應利用了至少一種羧化劑，此羧化劑選自二氧化碳、碳酸乙酯或碳酸甲酯、原甲酸酯等有機碳酸酯及氰化物(CN-)。Carboxylation reaction using at least one carboxylated agent, this agent is selected from carboxylated carbon dioxide, carbonate or ethyl methyl carbonate, orthoformate etc. organic carbonate and cyanide (CN-).
尤其是，進行羧化反應採用了任意形態(氣態、亞臨界、固態及液態)之二氧化碳。但是，亞臨界形態之二氧化碳優選用於羧化至少一個烷基團取代基芳族烴。而且，進行羧化反應可以利用能夠促進反應之任何適當的液體介質。此類液體介質包括但不限於直鏈或支鏈烷烴、環烷烴、鹵代烷烴及其混合物。In particular, the carboxylation reaction employs carbon dioxide in any form (gaseous, subcritical, solid, and liquid). However, the subcritical form of carbon dioxide is preferably used to carboxylate at least one alkyl group-substituted aromatic hydrocarbon. Moreover, the carboxylation reaction can utilize any suitable liquid medium capable of promoting the reaction. Such liquid media include, but are not limited to, linear or branched alkanes, cycloalkanes, halogenated alkanes, and mixtures thereof.
需要當心的是，要限制用於本公示目的之液體介質之水份含量範圍為1至100ppm，因為較高水份可能負面影響所用催化劑之活性。It is to be noted that the liquid content of the liquid medium used for the purpose of this disclosure is limited to a range of from 1 to 100 ppm, since higher moisture may adversely affect the activity of the catalyst used.
用於本公示目的之催化劑用式I表示；(AcBy)式IThe catalyst used for the purpose of this disclosure is represented by Formula I; (Ac By ) Formula I
式I中的A是一種金屬陽離子，包括但不限於鋁(Al)、鐵(Fe)、鎵(Ga)、銻(Sb)、鉬(Mo)及銅(Cu)。A in formula I is a metal cation including, but not limited to, aluminum (Al), iron (Fe), gallium (Ga), antimony (Sb), molybdenum (Mo), and copper (Cu).
式I中的B是一種陰離子，包括但不限於硫酸鹽(SO42-)、硝酸鹽(NO3-)、鉻酸鹽(CrO42-)、重鉻酸鹽(Cr2O72-)、高氯酸鹽(ClO4-)、高碘酸鹽(IO4-)、過溴酸鹽(BrO4-)、過硫酸鹽(S2O82-)等等。B in formula I is an anion including, but not limited to, sulfate (SO42- ), nitrate (NO3- ), chromate (CrO42- ), dichromate (Cr2 O72 - ), perchlorate (ClO4- ), periodate (IO4- ), perbromate (BrO4- ), persulfate (S2 O82- ) and the like.
x是範圍1至2之整數，代表陽離子數；y是範圍1至3之整數，代表陰離子數。x is an integer ranging from 1 to 2, representing the number of cations; y is an integer ranging from 1 to 3, representing the number of anions.
尤其是，將硝酸鋁(Al(NO3)3)用作催化劑，以實施本公示之方法。In particular, aluminum nitrate (Al(NO3 )3 ) is used as a catalyst to carry out the method of the present disclosure.
化合物之陽離子部份通常具有路易斯酸、強路易斯酸、超路易斯酸或任何形式之酸性或缺電子類之特徵，能夠提升CO2之活性及羧化反應之位點。The cationic portion of the compound typically has the characteristics of a Lewis acid, a strong Lewis acid, a super Lewis acid, or any form of acidic or electron deficient, which enhances the activity of the CO2 and the site of the carboxylation reaction.
化合物之陰離子部份通常具有吸電子性之特徵，使其能夠增強陽離子部份之路易斯酸性，也能夠作用為一種氧化劑。The anionic portion of the compound is generally characterized by electron-withdrawing properties, which enhances the Lewis acidity of the cationic moiety and acts as an oxidizing agent.
化合物之陰離子部份通常是一種去酸試劑，用式II表示；HxBv式IIThe anionic portion of the compound is typically a deacidification reagent, represented by Formula II; Hx Bv Formula II
式II中的H是氫。H in formula II is hydrogen.
式II中的B是一種陰離子，選自硫酸鹽(SO42-)、硝酸鹽(NO3-)、鉻酸鹽(CrO42-)、重鉻酸鹽(Cr2O72-)、高氯酸鹽(ClO4-)、高碘酸鹽(IO4-)、過溴酸鹽(BrO4-)、過硫酸鹽(S2O82-)。B in formula II is an anion selected from the group consisting of sulfate (SO42- ), nitrate (NO3- ), chromate (CrO42- ), dichromate (Cr2 O72- ) Perchlorate (ClO4- ), periodate (IO4- ), perbromate (BrO4- ), persulfate (S2 O82- ).
x和y是範圍1至2之整數。x and y are integers ranging from 1 to 2.
可以看出，儘管可以使用相比於反應物之催化劑之任意摩爾濃度，基於成本和反應效率之理由，所用催化劑摩爾濃度範圍是5至10%重量比。It can be seen that although any molar concentration of the catalyst compared to the reactants can be used, the molar concentration of the catalyst used is 5 to 5 based on cost and reaction efficiency.10% by weight.
在芳環之羧化反應過程中形成的氧化劑能夠進行附於羧化芳族產物之烷基團之氧化反應。所述氧化劑包括但不限於硫酸、硝酸、鉻酸、過乙酸及次氯酸。The oxidizing agent formed during the carboxylation reaction of the aromatic ring is capable of undergoing an oxidation reaction of an alkyl group attached to the carboxylated aromatic product. The oxidizing agents include, but are not limited to, sulfuric acid, nitric acid, chromic acid, peracetic acid, and hypochlorous acid.
進行羧化反應和氧化反應之溫度範圍是40℃至100℃，壓力範圍是500至900psi。The carboxylation and oxidation reactions are carried out at temperatures ranging from 40 ° C to 100 ° C and pressures ranging from 500 to 900 psi.
由於對本公示之方法中所用催化劑有負面影響，方法、尤其是羧化反應是在無水份條件下進行。無水份環境能夠透過使用惰性氣體來保持。Due to the negative effect on the catalyst used in the process of the present disclosure, the process, especially the carboxylation reaction, is carried out under anhydrous conditions. The anhydrous portion environment can be maintained by using an inert gas.
在芳族化合物或烷取代基芳族化合物中的烷基團(附帶至少一個烷基團)是C1至C5烷基團。尤其是，附帶至少一個烷基團之芳族化合物選自甲苯、鄰二甲苯、間二甲苯、對二甲苯及C2-烷基苯。而且，此類反應物經羧化反應獲得的羧化產物至少是甲苯甲酸、二甲基苯甲酸及單羧基芳族酮之一。The alkyl group (attached to at least one alkyl group) in the aromatic compound or the alkane-substituted aromatic compound is a C1 to C5 alkyl group. In particular, the aromatic compound bearing at least one alkyl group is selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene and C2 -alkylbenzene. Moreover, the carboxylated product obtained by the carboxylation reaction of such a reactant is at least one of toluic acid, dimethylbenzoic acid and monocarboxylic aromatic ketone.
再者，中間酸產物經氧化反應獲得的氧化產物是至少一種化合物，此化合物選自鄰苯二甲酸、對苯二甲酸和苯三羧酸。Further, the oxidation product obtained by the oxidation reaction of the intermediate acid product is at least one compound selected from the group consisting of phthalic acid, terephthalic acid and benzenetricarboxylic acid.
根據本公示之一個示例方案，提供了一種羧化氧化甲苯之整合方法，旨在獲得對苯二甲酸。According to an exemplary embodiment of the present disclosure, an integrated method of carboxylated oxidized toluene is provided to obtain terephthalic acid.
現借助以下非限定性實例來敍述本公示。The present disclosure is now described by way of the following non-limiting examples.
對比實例1：Comparison example 1:
10克苯添加到裝有2克無水氯化鋁之高壓反應器中。通入CO2增壓反應器至700psi及加熱至100℃。攪拌中反應持續4小時。反應結束時釋放CO2及用乙酸乙酯萃取混合物。用1680cm-1處之FTIR峰值確認存在甲苯甲酸，包括在Ind,Eng Chem Res,2009,48,1059中提及之其他特徵物。Ten grams of benzene was added to a high pressure reactor containing 2 grams of anhydrous aluminum chloride. The CO2 pressurized reactor was passed to 700 psi and heated to 100 °C. The reaction was continued for 4 hours with stirring. At the end of the reaction, CO2 was released and the mixture was extracted with ethyl acetate. The presence of toluic acid was confirmed by the FTIR peak at 1680 cm-1 , including other features mentioned in Ind, Eng Chem Res, 2009, 48, 1059.
對比實例2：Comparison example 2:
以相同於對比實例1之方式實施本實例，但用甲苯替換苯以獲得甲苯甲酸產品。The present example was carried out in the same manner as in Comparative Example 1, except that benzene was replaced with toluene to obtain a toluic acid product.
本發明實例3：Example 3 of the present invention:
以相同於對比實例2之方式實施本實例，但使用2.54克硝酸鋁以獲得苯二羧酸，即對苯二甲酸及鄰苯二甲酸。對苯二甲酸與鄰苯二甲酸之比例為97：3。用FTIR確認存在對苯二甲酸及鄰苯二甲酸。The present example was carried out in the same manner as in Comparative Example 2 except that 2.54 g of aluminum nitrate was used to obtain benzenedicarboxylic acid, i.e., terephthalic acid and phthalic acid. The ratio of terephthalic acid to phthalic acid is 97:3. The presence of terephthalic acid and phthalic acid was confirmed by FTIR.
技術先進性：Technological advancement:
本公示涉及一種羧化及氧化有機化合物之整合方法，旨在一個連續步驟中製備聚羧酸，此方法免去了在低溫條件下使用大量試劑，從而使其經濟及環境友好。The present disclosure relates to a method for the integration of carboxylated and oxidized organic compounds, which is directed to the preparation of polycarboxylic acids in a continuous step which eliminates the use of large amounts of reagents at low temperatures, thereby making them economical and environmentally friendly.
在本說明書全文，應理解“包括”或“含有”一詞之含義是包括所陳述的單個元素、整體或步驟，也可以是包括多個元素、整體或步驟，但並不排除任何其他單個元素、整體或步驟，也不排除其他多個元素、整體或步驟。Throughout the specification, the meaning of the words "including" or "comprising" is intended to include the singular or s , whole or step, does not exclude other elements, wholes or steps.
本說明書中所有關於文檔、法案、材料、設備、文獻等之論述，其唯一目的是為本發明提供理據。不應將其視為承認，任何或所有此類事項形成了先有技術基礎之一部份或因其在本申請優先日之前已經存在而是本發明相關領域之公知常識。All statements in this specification regarding documents, acts, materials, equipment, literature, etc., are solely intended to provide a basis for the present invention. It should not be considered as an admission that any or all such matters form part of the prior art basis or the common general knowledge of the field in which the invention pertains.
所提及各種物理參數、外形尺寸或數量之數值僅僅是近似值，可以設想，凡大於/小於分配給此類參數、外形尺寸或數量之數值都應該在本發明範圍內，除非在具體說明書中有相反的陳述。The values of various physical parameters, dimensions, or quantities referred to are merely approximations, and it is contemplated that values greater than/less than those assigned to such parameters, dimensions, or quantities should be within the scope of the invention, unless otherwise specified in the specification. The opposite statement.
透過引用本說明書中的非限定性方案，本文詳細說明了此類方案之特點和優點。說明中省略了公知的構件和加工方法，避免本文方案顯得模糊。本文之舉例只圖便於理解實施本文方案之方式，進而使本領域技術人員能夠實施本文方案。由此可見，此類實例不應詮釋為限定本文方案之範圍。The features and advantages of such schemes are described in detail by reference to non-limiting aspects of this specification. Known components and processing methods are omitted from the description to avoid obscuring the scheme. The examples herein are only to facilitate an understanding of the manner in which the embodiments herein are implemented, and thus, those skilled in the art can implement the embodiments herein. Thus, such examples are not to be construed as limiting the scope of the embodiments herein.
以上關於具體方案之敍述充分揭示了本文方案之一般性質，使其他人能夠應用現有知識，在不脫離一般概念情況下，輕鬆修改及/或調整以適合各種應用，因此，應該且意圖理解此類調整和修改是在等同所公開方案之意思和範圍內。應該理解，本文所用措辭或術語是用於敍述而非限定目的。因此，儘管本文方案措辭以“優選方案”進行敍述，本領域技術人員將會認同，在本文所述方案之精神和範圍內，本文方案能夠在實施中修改。The above description of the specific scheme fully reveals the general nature of the scheme, so that others can apply the existing knowledge, easily modify and / or adjust to suit various applications without departing from the general concept, therefore, should and intend to understand such Adjustments and modifications are within the meaning and range of equivalents. It will be understood that the phraseology or terminology used herein is for the purposes of the description Accordingly, the present disclosure is to be construed as being limited to the details of the embodiments herein.
“但凡規定了值的某個範圍，低於或高於規定範圍之最低或最高值達10%之某個值包括在本公示之範圍內”。儘管本文著重強調優選方案，在不脫離本公示之原則下，認可制訂許多其他方案，認可對優選方案進行許多更改。對本領域技術人員而言，顯然可以根據本公示之內容，對本公示之優選方案和其他方案進行如此這般之更改，為此，應清楚地理解，本文敍述的事項，只是對本公示進行說明，而不是對其進行限定。“When a range of values is specified, a value below or above 10% of the minimum or maximum value of the specified range is included in the scope of this publication”. While the present invention emphasizes the preferred embodiment, many other alternatives are recognized without departing from the principles of this disclosure, and many modifications are made to the preferred embodiment. It is obvious to those skilled in the art that the present invention can be modified in such a manner and other aspects in accordance with the contents of the present disclosure. For this reason, it should be clearly understood that the matters described herein are merely illustrative of the present disclosure. It is not limited.
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| TW103124026ATWI640503B (en) | 2013-07-12 | 2014-07-11 | An integrated process for carboxylation and oxidation of alkyl substituted aromatic hydrocarbons |
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| TW (1) | TWI640503B (en) |
| WO (1) | WO2015004683A2 (en) |
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