CN104072338B - A kind of method preparing pyrocatechol - Google Patents
A kind of method preparing pyrocatechol Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及一种制备邻苯二酚的方法。The invention relates to a method for preparing catechol.
背景技术Background technique
邻苯二酚，又叫儿茶酚，水果及蔬菜中通常存在的有机酚，是植物鞣质的成分。邻苯二酚是重要的化工中间体，可用于制造橡胶硬化剂、电镀添加剂、皮肤防腐杀菌剂、染发剂和照相显影剂等。Catechol, also known as catechol, is an organic phenol commonly found in fruits and vegetables, and is a component of plant tannins. Catechol is an important chemical intermediate, which can be used in the manufacture of rubber hardeners, electroplating additives, skin antiseptics, hair dyes, and photographic developers.
CN1160703A公开了一种邻苯二酚的生产方法，是用双氧水在甲酸存在下氧化环己烯，而后直接加碱进行中和，水解成1,2-环己二醇，再用乙酸乙醋萃取，然后蒸除溶剂而获得1,2-环己二醇，然后在装有Ni/硅藻土催化剂的固定床上通入汽化、过热的1,2环己二醇水溶液蒸气，进行催化脱氢而得邻苯二酚，反应30h之后脱氢催化剂失活需要再生脱氢催化剂。该方法步骤繁多，尤其脱氢工艺使用汽化、过热的1,2环己二醇水溶液蒸气，需要消耗大量热量去气化加热水，能量利用率极低。CN1160703A discloses a production method of catechol, which is to oxidize cyclohexene with hydrogen peroxide in the presence of formic acid, then directly add alkali to neutralize, hydrolyze into 1,2-cyclohexanediol, and then extract with ethyl acetate , and then evaporate the solvent to obtain 1,2-cyclohexanediol, and then pass through the vaporized and superheated 1,2-cyclohexanediol aqueous solution vapor on the fixed bed equipped with Ni/diatomaceous earth catalyst, and carry out catalytic dehydrogenation to obtain To obtain catechol, the deactivation of the dehydrogenation catalyst after 30 hours of reaction requires regeneration of the dehydrogenation catalyst. The method has a lot of steps, especially the dehydrogenation process uses vaporized and superheated 1,2-cyclohexanediol aqueous solution vapor, which needs to consume a lot of heat to gasify and heat water, and the energy utilization rate is extremely low.
发明内容Contents of the invention
本发明的目的是在现有技术的基础上提供一种能耗低的制备邻苯二酚的方法，且该方法1,2-环己二醇转化率高，邻苯二酚选择性高，并且可以进行连续生产。The purpose of the present invention is to provide a method for preparing catechol with low energy consumption on the basis of the prior art, and the method 1,2-cyclohexanediol conversion rate is high, and catechol selectivity is high, And can carry out continuous production.
本发明的发明人发现，按照现有技术的采用装有Ni/硅藻土催化剂的固定床上通入汽化、过热的1,2环己二醇水溶液蒸气，进行催化脱氢而得邻苯二酚，消耗大量的能源，同时催化剂寿命仅30h，催化剂再生工艺复杂难度较大。The inventors of the present invention have found that, according to the prior art, the vaporized and superheated 1,2 cyclohexanediol aqueous solution steam is introduced into a fixed bed equipped with a Ni/diatomaceous earth catalyst to carry out catalytic dehydrogenation to obtain catechol , consumes a lot of energy, and at the same time, the catalyst life is only 30h, and the catalyst regeneration process is complicated and difficult.
同时，以环己烯作为原料制备邻苯二酚的方法，首先通过氧化环己烯制备1,2-环己二醇，然后经过萃取、蒸馏等步骤得到1,2-环己二醇，然后将1,2-环己二醇进行脱氢得到邻苯二酚，按照该方法制备领苯二酚，由于在工业应用过程中溶剂等用量均非常大，由此造成萃取或蒸馏的能耗非常高，从而大大降低了其工业应用价值，而本发明的发明人试图设想能否不分离，而直接将氧化环己烯得到的主要包含1,2-环己二醇的液相产物进行脱氢制备邻苯二酚，如此可以大大降低能耗，且能大大节约操作工序，而将这种设想进行试验发现，由于氧化脱氢得到的液相产物中含有大量的由氧化催化剂带来的阴离子和阳离子影响了后续的脱氢催化剂的脱氢活性，导致脱氢过程效率很低，使得按照该方法无法高效的制备得到邻苯二酚；在此基础上，本发明的发明人提出，除去液相产物中的由氧化催化剂带来的阴离子和阳离子，如此可以避免其影响后续的脱氢过程中的脱氢催化剂的活性，同时后续的脱氢工艺使用液相脱氢技术，不仅不需要气化大量的水和原料，同时液相反应中反应物不易在催化剂上结焦，大大延长了催化剂的寿命，从而可以高效的制备得到邻苯二酚，而克服了由于邻苯二酚极易结焦导致催化剂易失活而不能连续有效的批量生产的缺陷。基于前述发明思路，完成了本发明。Meanwhile, the method for preparing catechol with cyclohexene as a raw material first prepares 1,2-cyclohexanediol by oxidizing cyclohexene, then obtains 1,2-cyclohexanediol through steps such as extraction and distillation, and then Dehydrogenate 1,2-cyclohexanediol to obtain catechol, and prepare catechol according to this method. Since the amount of solvent and the like is very large in the industrial application process, the energy consumption of extraction or distillation is very high. High, thereby greatly reducing its industrial application value, and the inventors of the present invention try to imagine whether it is not possible to separate, and directly dehydrogenate the liquid phase product mainly comprising 1,2-cyclohexanediol obtained by oxidizing cyclohexene The preparation of catechol can greatly reduce energy consumption and greatly save operating procedures, and it is found that the liquid phase product obtained by oxidative dehydrogenation contains a large amount of anions and The cation affects the dehydrogenation activity of the subsequent dehydrogenation catalyst, resulting in a very low efficiency of the dehydrogenation process, making it impossible to efficiently prepare catechol according to this method; on this basis, the inventors of the present invention proposed that the liquid phase The anions and cations brought by the oxidation catalyst in the product can avoid affecting the activity of the dehydrogenation catalyst in the subsequent dehydrogenation process. At the same time, the reactants in the liquid phase reaction are not easy to coke on the catalyst, which greatly prolongs the life of the catalyst, so that catechol can be efficiently prepared, and it overcomes the easy coking of catechol and the easy coking of the catalyst. Defects that cannot be continuously and effectively mass-produced due to inactivation. Based on the aforementioned inventive ideas, the present invention has been accomplished.
为实现前述目的，本发明提供了一种制备邻苯二酚的方法，该方法包括：To achieve the aforementioned object, the invention provides a method for preparing pyrocatechol, the method comprising:
（1）在将环己烯氧化为1,2-环己二醇的反应条件下，将环己烯、氧化剂与催化剂接触得到含1,2-环己二醇的反应液，脱除所述反应液中的阴离子和阳离子，得到脱氢原液；(1) Under the reaction conditions of oxidizing cyclohexene to 1,2-cyclohexanediol, contact cyclohexene, an oxidant and a catalyst to obtain a reaction solution containing 1,2-cyclohexanediol, and remove the anions and cations in the reaction solution to obtain a dehydrogenation stock solution;
（2）在液相催化脱氢条件下，将所述脱氢原液与脱氢催化剂接触。(2) Under the condition of liquid-phase catalytic dehydrogenation, the dehydrogenation stock solution is contacted with a dehydrogenation catalyst.
按照本发明的方法无需提纯出1,2-环己二醇再进行脱氢制备邻苯二酚，可以直接采用液相脱氢技术进行脱氢，使得不仅不需要气化大量的溶剂和原料，同时液相反应中反应物不易在催化剂上结焦，大大延长了催化剂的寿命，从而可以高效的制备得到邻苯二酚。由此使得按照本发明的方法制备邻苯二酚的能耗大大降低，且邻苯二酚的收率很高。由此可见，本发明的方法非常具有工业应用价值。According to the method of the present invention, there is no need to purify 1,2-cyclohexanediol and then dehydrogenate to prepare catechol, and liquid phase dehydrogenation technology can be directly used for dehydrogenation, so that not only does not need to gasify a large amount of solvents and raw materials, At the same time, the reactants in the liquid phase reaction are not easy to coke on the catalyst, which greatly prolongs the life of the catalyst, so that catechol can be efficiently prepared. Therefore, the energy consumption of preparing catechol according to the method of the present invention is greatly reduced, and the yield of catechol is very high. This shows that the method of the present invention has industrial application value very much.
具体实施方式Detailed ways
本发明提供了一种制备邻苯二酚的方法，该方法包括：（1）在将环己烯氧化为1,2-环己二醇的反应条件下，将环己烯、氧化剂与催化剂接触得到含1,2-环己二醇的反应液，脱除所述反应液中的阴离子和阳离子，得到脱氢原液；（2）在液相催化脱氢条件下，将所述脱氢原液与脱氢催化剂接触。The invention provides a method for preparing catechol, the method comprising: (1) under the reaction conditions for oxidizing cyclohexene to 1,2-cyclohexanediol, contacting cyclohexene and an oxidizing agent with a catalyst Obtaining a reaction solution containing 1,2-cyclohexanediol, removing anions and cations in the reaction solution to obtain a dehydrogenation stock solution; (2) under liquid-phase catalytic dehydrogenation conditions, combining the dehydrogenation stock solution with dehydrogenation catalyst contact.
本发明中，所述阴离子和阳离子指的是会影响本发明的步骤（2）的脱氢催化剂活性的阴离子和阳离子。In the present invention, the anions and cations refer to anions and cations that may affect the activity of the dehydrogenation catalyst in step (2) of the present invention.
本发明中，脱除所述含1,2-环己二醇的反应液中的阴离子和阳离子的方法有多种，针对本发明，为了节约成本，优选脱除所述含1,2-环己二醇的反应液中的阴离子和阳离子的方法包括如下步骤：将所述含1,2-环己二醇的反应液按照正序或反序经过阳离子交换树脂和阴离子交换树脂。例如若需要先脱除所述含1,2-环己二醇的反应液中的阳离子，则可以先将所述含1,2-环己二醇的反应液与阳离子交换树脂接触脱除阳离子，而若需要先脱除所述含1,2-环己二醇的反应液中的阴离子，则可以先将所述含1,2-环己二醇的反应液与阴离子交换树脂接触脱除阴离子，事实上，本发明不要求所述阳离子和阴离子的脱除顺序，只要保证最后经过阳离子交换树脂和阴离子交换树脂后，含1,2-环己二醇的反应液中不含阴离子和阳离子即可。In the present invention, there are many ways to remove the anions and cations in the reaction solution containing 1,2-cyclohexanediol. For the present invention, in order to save costs, it is preferred to remove the 1,2-cyclohexanediol containing The method for anion and cation in the reaction solution of hexanediol comprises the following steps: passing the reaction solution containing 1,2-cyclohexanediol through a cation exchange resin and an anion exchange resin in a forward sequence or a reverse sequence. For example, if the cations in the reaction solution containing 1,2-cyclohexanediol need to be removed first, the reaction solution containing 1,2-cyclohexanediol can be contacted with a cation exchange resin to remove cations first. , and if the anions in the reaction solution containing 1,2-cyclohexanediol need to be removed first, the reaction solution containing 1,2-cyclohexanediol can be contacted with an anion exchange resin to remove Anion, in fact, the present invention does not require the removal sequence of the cation and anion, as long as it is ensured that the reaction solution containing 1,2-cyclohexanediol does not contain anion and cation after passing through the cation exchange resin and the anion exchange resin That's it.
本发明中，所述阳离子交换树脂的种类的可选范围较宽，现有技术的能够用于脱去阳离子的阳离子交换树脂均可用于本发明，本发明对此无特殊要求，在此不再详细描述。具体可以根据阳离子的种类进行选择。In the present invention, the optional range of the kind of described cation-exchange resin is wider, and the cation-exchange resin that can be used for removing cation in the prior art can all be used in the present invention, and the present invention has no special requirement to this, no longer A detailed description. Specifically, it can be selected according to the type of cation.
本发明中，所述阴离子交换树脂的种类的可选范围较宽，现有技术的能够用于脱去阴离子的阴离子交换树脂均可用于本发明，本发明对此无特殊要求，在此不再详细描述。具体可以根据阴离子的种类进行选择。In the present invention, the optional range of the kind of described anion-exchange resin is wider, and the anion-exchange resin that can be used for removing anions in the prior art can all be used in the present invention, and the present invention has no special requirement to this, no longer A detailed description. Specifically, it can be selected according to the type of anion.
根据本发明的方法，步骤（1）中所述将环己烯氧化为1,2-环己二醇的反应条件一般包括：pH值在5以下，即步骤（1）中所述接触在酸性条件下进行，具体地，在具体实施过程中，若含有所述氧化剂、催化剂和环己烯的反应体系不具备酸性，此时可以通过额外加入酸性物质到所述反应体系中调节反应体系的pH值。According to the method of the present invention, the reaction conditions for oxidizing cyclohexene to 1,2-cyclohexanediol in step (1) generally include: the pH value is below 5, that is, the contact in step (1) is under acidic Under conditions, specifically, in the specific implementation process, if the reaction system containing the oxidant, catalyst and cyclohexene does not have acidity, the pH of the reaction system can be adjusted by adding an additional acidic substance to the reaction system. value.
更优选，步骤（1）中所述将环己烯氧化为1,2-环己二醇的反应条件还包括：温度为30-100℃，优选为50-80℃，优选为60℃。More preferably, the reaction conditions for oxidizing cyclohexene to 1,2-cyclohexanediol in step (1) further include: a temperature of 30-100°C, preferably 50-80°C, preferably 60°C.
根据本发明的方法，步骤（1）中所述氧化剂的种类的可选范围较宽，现有技术常用的用于将环己烯氧化为1,2-环己二醇的氧化剂均可用于本发明，针对本发明优选所述氧化剂为过氧化氢或过氧化氢水溶液。According to the method of the present invention, the optional range of the oxidizing agent described in step (1) is relatively wide, and the oxidizing agent commonly used in the prior art for oxidizing cyclohexene to 1,2-cyclohexanediol can be used in this method. Invention, for the present invention, it is preferred that the oxidizing agent is hydrogen peroxide or an aqueous hydrogen peroxide solution.
根据本发明的方法，所述催化剂的种类的可选范围较宽，现有技术的能够用于将环己烯氧化为1,2-环己二醇的催化剂均可用于本发明，针对本发明，优选催化剂为钛硅分子筛、杂多酸盐和酸性催化剂中的一种或多种；其中，所述酸性催化剂优选为硫酸、磷酸、氟硼酸和苯磺酸中的一种或多种。According to the method of the present invention, the optional range of the type of the catalyst is wide, and the catalysts in the prior art that can be used to oxidize cyclohexene to 1,2-cyclohexanediol can be used in the present invention, and for the present invention , preferably the catalyst is one or more of titanium-silicon molecular sieves, heteropolyacid salts and acidic catalysts; wherein, the acidic catalyst is preferably one or more of sulfuric acid, phosphoric acid, fluoboric acid and benzenesulfonic acid.
根据本发明的一种优选的实施方式，优选步骤（1）中所述氧化剂为过氧化氢水溶液，所述催化剂为钛硅分子筛；所述将环己烯氧化为1,2-环己二醇的反应条件包括：接触的pH值在5以下，温度为30-100℃，时间为2-20h，环己烯与过氧化氢的摩尔比为1:（0.2-1.2），钛硅分子筛与环己烯的质量比为0.001-0.1:1。更优选所述接触在溶剂存在下进行，所述溶剂的种类的可选范围较宽，现有技术使用的溶剂均可用于本发明，例如可以为水、烷烃、醇、酮、腈、酯和卤代烃中的一种或多种。而为了减小溶剂对两组反应（包括步骤（1）和步骤（2））的影响，优选所述溶剂为二甲苯、甲苯、乙醇、丙醇、乙二醇、丙二醇、环己醇、丁二醇、辛醇、乙酸乙酯、乙二醇二己酸酯、乙二醇二乙酸酯、丁二醇二乙酸酯、己二酸二乙酯、邻苯二甲酸丁酯、乙腈、己二腈、环己酮、丙酮、异佛尔酮和水中的一种或多种。更优选所述有机溶剂与环己烯的质量比为（1-30）:1。且如前所述，由于前述反应体系不具备所要求的pH值，因此可以通过向反应体系中加入酸性物质进行调节接触所需的pH值。According to a preferred embodiment of the present invention, the oxidizing agent described in the preferred step (1) is hydrogen peroxide aqueous solution, and the catalyst is titanium silicon molecular sieve; the oxidation of cyclohexene to 1,2-cyclohexanediol The reaction conditions include: the contact pH value is below 5, the temperature is 30-100°C, the time is 2-20h, the molar ratio of cyclohexene to hydrogen peroxide is 1: (0.2-1.2), titanium silicon molecular sieve and ring The mass ratio of hexene is 0.001-0.1:1. More preferably described contact is carried out under the presence of solvent, and the optional range of the kind of described solvent is wider, and the solvent that prior art uses all can be used in the present invention, for example can be water, alkane, alcohol, ketone, nitrile, ester and One or more of halogenated hydrocarbons. And in order to reduce the influence of solvent on two groups of reactions (comprising step (1) and step (2)), preferably described solvent is xylene, toluene, ethanol, propanol, ethylene glycol, propylene glycol, cyclohexanol, butane Glycol, octanol, ethyl acetate, ethylene glycol dicaproate, ethylene glycol diacetate, butanediol diacetate, diethyl adipate, butyl phthalate, acetonitrile, One or more of adiponitrile, cyclohexanone, acetone, isophorone and water. More preferably, the mass ratio of the organic solvent to cyclohexene is (1-30):1. And as mentioned above, since the aforementioned reaction system does not have the required pH value, the pH value required for the contact can be adjusted by adding acidic substances into the reaction system.
脱氢催化剂可以为现有技术的各种脱氢催化剂，例如可以为镍系脱氢催化剂、钯系脱氢催化剂、铂系脱氢催化剂、钌系脱氢催化剂和铑系脱氢催化剂中的一种或多种。The dehydrogenation catalyst can be various dehydrogenation catalysts of the prior art, for example, can be one of nickel-based dehydrogenation catalyst, palladium-based dehydrogenation catalyst, platinum-based dehydrogenation catalyst, ruthenium-based dehydrogenation catalyst and rhodium-based dehydrogenation catalyst one or more species.
根据本发明的方法，步骤（2）中所述脱氢催化剂的活性组分含有第Ⅷ族金属元素，针对本发明，优选所述第Ⅷ族金属元素为镍元素、钯元素、铂元素、钌元素和铑元素中的一种或多种，因此针对本发明，优选所述含有第Ⅷ族金属元素的脱氢催化剂为镍系脱氢催化剂、钯系脱氢催化剂、铂系脱氢催化剂、钌系脱氢催化剂和铑系脱氢催化剂中的一种或多种。According to the method of the present invention, the active component of the dehydrogenation catalyst in step (2) contains Group VIII metal elements. For the present invention, the Group VIII metal elements are preferably nickel, palladium, platinum, ruthenium element and rhodium element, so for the present invention, preferably the dehydrogenation catalyst containing Group VIII metal element is a nickel-based dehydrogenation catalyst, palladium-based dehydrogenation catalyst, platinum-based dehydrogenation catalyst, ruthenium One or more of dehydrogenation catalysts and rhodium-based dehydrogenation catalysts.
本发明中，优选所述镍系脱氢催化剂为中，镍含量为10-95重量%，脱氢助剂组分的含量为1-15重量%，其它为载体。其中，所述脱氢助剂组分优选为碱金属硫酸盐、碱金属碳酸盐、碱土金属硫酸盐和碱土金属碳酸盐中的一种或多种，更优选为硫酸钠、硫酸钾、硫酸锂、硫酸镁、硫酸钙、碳酸钠、硫酸钡、碳酸钾和碳酸锂中的一种或多种；所述载体优选为二氧化硅、三氧化二铝和活性炭中的一种或多种。In the present invention, preferably, the nickel-based dehydrogenation catalyst is medium, the nickel content is 10-95% by weight, the content of the dehydrogenation aid component is 1-15% by weight, and the others are carriers. Wherein, the dehydrogenation aid component is preferably one or more of alkali metal sulfate, alkali metal carbonate, alkaline earth metal sulfate and alkaline earth metal carbonate, more preferably sodium sulfate, potassium sulfate, One or more in lithium sulfate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, potassium carbonate and lithium carbonate; Described carrier is preferably one or more in silicon dioxide, aluminum oxide and gac .
本发明中，优选所述钯系脱氢催化剂中，钯含量为0.3-6重量%，脱氢助剂组分的含量为1-15重量%，其它为载体。其中，所述脱氢助剂组分优选为碱金属硫酸盐、碱金属碳酸盐、碱土金属硫酸盐和碱土金属碳酸盐中的一种或多种，更优选为硫酸钠、硫酸钾、硫酸锂、硫酸镁、硫酸钙、碳酸钠、硫酸钡、碳酸钾和碳酸锂中的一种或多种；所述载体优选为二氧化硅、三氧化二铝和活性炭中的一种或多种。其制备方法可以采用本领域常规的制备方法，本发明在此不详细描述。In the present invention, preferably, in the palladium-based dehydrogenation catalyst, the palladium content is 0.3-6% by weight, the content of the dehydrogenation aid component is 1-15% by weight, and the others are carriers. Wherein, the dehydrogenation aid component is preferably one or more of alkali metal sulfate, alkali metal carbonate, alkaline earth metal sulfate and alkaline earth metal carbonate, more preferably sodium sulfate, potassium sulfate, One or more in lithium sulfate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, potassium carbonate and lithium carbonate; Described carrier is preferably one or more in silicon dioxide, aluminum oxide and gac . Its preparation method can adopt conventional preparation methods in the art, and the present invention will not be described in detail here.
本发明中，优选所述铂系脱氢催化剂中，铂含量为0.3-6重量%，脱氢助剂组分的含量为1-15重量%，其它为载体。其中，所述脱氢助剂组分优选为碱金属硫酸盐、碱金属碳酸盐、碱土金属硫酸盐和碱土金属碳酸盐中的一种或多种，更优选为硫酸钠、硫酸钾、硫酸锂、硫酸镁、硫酸钙、碳酸钠、硫酸钡、碳酸钾和碳酸锂中的一种或多种；所述载体优选为二氧化硅、三氧化二铝和活性炭中的一种或多种。其制备方法可以采用本领域常规的制备方法，本发明在此不详细描述。In the present invention, preferably, in the platinum-based dehydrogenation catalyst, the platinum content is 0.3-6% by weight, the content of the dehydrogenation aid component is 1-15% by weight, and the others are carriers. Wherein, the dehydrogenation aid component is preferably one or more of alkali metal sulfate, alkali metal carbonate, alkaline earth metal sulfate and alkaline earth metal carbonate, more preferably sodium sulfate, potassium sulfate, One or more in lithium sulfate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, potassium carbonate and lithium carbonate; Described carrier is preferably one or more in silicon dioxide, aluminum oxide and gac . Its preparation method can adopt conventional preparation methods in the art, and the present invention will not be described in detail here.
本发明中，优选所述钌系脱氢催化剂中，钌含量为0.3-10重量%，脱氢助剂组分的含量为1-15重量%，其它为载体。其中，所述助剂优选为碱金属硫酸盐、碱金属碳酸盐、碱土金属硫酸盐和碱土金属碳酸盐中的一种或多种，更优选为硫酸钠、硫酸钾、硫酸锂、硫酸镁、硫酸钙、碳酸钠、硫酸钡、碳酸钾和碳酸锂中的一种或多种；所述载体优选为二氧化硅、三氧化二铝和活性炭中的一种或多种。其制备方法可以采用本领域常规的制备方法，本发明在此不详细描述。In the present invention, preferably in the ruthenium-based dehydrogenation catalyst, the content of ruthenium is 0.3-10% by weight, the content of the dehydrogenation aid component is 1-15% by weight, and the others are carriers. Wherein, the auxiliary agent is preferably one or more of alkali metal sulfate, alkali metal carbonate, alkaline earth metal sulfate and alkaline earth metal carbonate, more preferably sodium sulfate, potassium sulfate, lithium sulfate, sulfuric acid One or more of magnesium, calcium sulfate, sodium carbonate, barium sulfate, potassium carbonate and lithium carbonate; the carrier is preferably one or more of silicon dioxide, aluminum oxide and activated carbon. Its preparation method can adopt conventional preparation methods in the art, and the present invention will not be described in detail here.
本发明中，优选所述铑系脱氢催化剂中，铑含量为0.3-10重量%，脱氢助剂组分的含量为1-15重量%，其它为载体。其中，所述脱氢助剂组分优选为碱金属硫酸盐、碱金属碳酸盐、碱土金属硫酸盐和碱土金属碳酸盐中的一种或多种，更优选为硫酸钠、硫酸钾、硫酸锂、硫酸镁、硫酸钙、碳酸钠、硫酸钡、碳酸钾和碳酸锂中的一种或多种；所述载体优选为二氧化硅、三氧化二铝和活性炭中的一种或多种其制备方法可以采用本领域常规的制备方法，本发明在此不详细描述。In the present invention, preferably, in the rhodium-based dehydrogenation catalyst, the rhodium content is 0.3-10% by weight, the content of the dehydrogenation aid component is 1-15% by weight, and the others are carriers. Wherein, the dehydrogenation aid component is preferably one or more of alkali metal sulfate, alkali metal carbonate, alkaline earth metal sulfate and alkaline earth metal carbonate, more preferably sodium sulfate, potassium sulfate, One or more in lithium sulfate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, potassium carbonate and lithium carbonate; Described carrier is preferably one or more in silicon dioxide, aluminum oxide and gac Its preparation method can adopt conventional preparation methods in the art, and the present invention will not be described in detail here.
根据本发明的方法，优选步骤（2）中所述液相催化脱氢条件包括：环己二醇液相催化脱氢，温度为170-350℃，脱氢催化剂与脱氢原液的质量比为1:5-200。在前述催化脱氢条件下，能够进一步提高按照本发明的方法的脱氢效率。According to the method of the present invention, the liquid-phase catalytic dehydrogenation conditions described in step (2) preferably include: liquid-phase catalytic dehydrogenation of cyclohexanediol, the temperature is 170-350 ° C, and the mass ratio of the dehydrogenation catalyst to the dehydrogenation stock solution is 1:5-200. Under the aforementioned catalytic dehydrogenation conditions, the dehydrogenation efficiency of the method according to the invention can be further increased.
本发明中，如未特别说明，所述接触均在搅拌条件下进行。In the present invention, unless otherwise specified, the contacting is carried out under stirring conditions.
下面通过实施例详细说明本发明，但本发明不局限于此。The present invention will be described in detail below through examples, but the present invention is not limited thereto.
本发明中，采用气相色谱进行体系中各组成的分析，通过校正归一法进行定量，均可参照现有技术进行，在此基础上计算反应物的转化率、产物的收率和选择性等评价指标。In the present invention, adopt gas chromatography to carry out the analysis of each composition in the system, carry out quantification by calibration normalization method, all can refer to prior art to carry out, calculate the conversion rate of reactant, the yield of product and selectivity etc. on this basis evaluation index.
本发明中，反应物转化率计算公式如下：In the present invention, the formula for calculating the conversion rate of the reactant is as follows:
组分选择性的计算公式如下：The formula for calculating component selectivity is as follows:
其中，X为转化率；S为选择性；m为组分的质量；n为组分的物质的量；其中m0和n0分表示相应反应前的质量和摩尔量。Among them, X is the conversion rate; S is the selectivity; m is the quality of the component; n is the amount of the component; where m 0 and n 0 points represent the mass and molar amount before the corresponding reaction.
本发明的实施例中，催化剂均为按照现有技术的方法合成或者商购得到。In the examples of the present invention, the catalysts are all synthesized according to the methods of the prior art or obtained commercially.
实施例1Example 1
（1）以丙酮作为有机溶剂，将环己烯、双氧水（30质量%）与钛硅分子筛TS-1接触，其中，环己烯与以过氧化氢计的双氧水的摩尔比为1:1.2，丙酮、钛硅分子筛与环己烯的质量比为15:0.05:1，且加入盐酸调节pH值为4，在60℃下接触3h，得到含1,2-环己二醇的反应液（环己烯转化率98.1%，1,2-环己二醇选择性98.8%），将所述含1,2-环己二醇的反应液中依次经过阳离子交换树脂和阴离子交换树脂脱除其中的阴离子（例如氯离子等）和阳离子（例如钛离子等），得到脱氢原液；(1) Using acetone as an organic solvent, contact cyclohexene and hydrogen peroxide (30% by mass) with titanium-silicon molecular sieve TS-1, wherein the molar ratio of cyclohexene to hydrogen peroxide calculated as hydrogen peroxide is 1:1.2, The mass ratio of acetone, titanium silicon molecular sieve and cyclohexene is 15:0.05:1, and hydrochloric acid is added to adjust the pH value to 4, and they are contacted at 60°C for 3 hours to obtain a reaction solution containing 1,2-cyclohexanediol (cyclohexanediol The conversion rate of hexene is 98.1%, the selectivity of 1,2-cyclohexanediol is 98.8%), the reaction liquid containing 1,2-cyclohexanediol is successively passed through cation exchange resin and anion exchange resin to remove the Anions (such as chloride ions, etc.) and cations (such as titanium ions, etc.) to obtain a dehydrogenation stock solution;
（2）将脱氢催化剂装入反应釜中，然后将所述脱氢原液引入到反应釜中与脱氢催化剂接触，在液相催化脱氢条件下进行催化脱氢，反应结果见表1。(2) Put the dehydrogenation catalyst into the reaction kettle, then introduce the dehydrogenation stock solution into the reaction kettle to contact with the dehydrogenation catalyst, and carry out catalytic dehydrogenation under the condition of liquid-phase catalytic dehydrogenation. The reaction results are shown in Table 1.
实施例2Example 2
按照实施例1的方法制备邻苯二酚，不同的是，步骤（2）的液相催化脱氢条件改变，以及结果见表1。Catechol was prepared according to the method of Example 1, except that the liquid-phase catalytic dehydrogenation conditions in step (2) were changed, and the results are shown in Table 1.
表1Table 1
对比例1Comparative example 1
按照实施例1的方法制备邻苯二酚，不同的是，将步骤（1）所得反应液不经过阳离子交换树脂和阴离子交换树脂，直接进行步骤（2）的脱氢，其余条件均相同，其中，1,2-环己二醇转化率为30%，邻苯二酚选择性为63.3%。According to the method of Example 1 to prepare catechol, the difference is that the reaction solution obtained in step (1) is directly dehydrogenated in step (2) without passing through cation exchange resin and anion exchange resin, and the rest of the conditions are the same, wherein , the conversion rate of 1,2-cyclohexanediol was 30%, and the selectivity of catechol was 63.3%.
由实施例的结果可知，采用本发明的方法使用环己烯制备邻苯二酚，邻苯二酚选择性高，并且无需经过中间的分离步骤，简化了操作过程并有效节约了能耗。It can be seen from the results of the examples that the method of the present invention uses cyclohexene to prepare catechol, which has high selectivity to catechol and does not need to go through intermediate separation steps, which simplifies the operation process and effectively saves energy consumption.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.
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