本发明属于电催化技术领域，尤其涉及一种离场电催化反应方法和反应系统。The invention belongs to the technical field of electrocatalysis, and in particular relates to an off-site electrocatalytic reaction method and a reaction system.
风、光、水、潮汐热等可再生资源可用于生产绿电。使用绿电，通过电催化技术可用于有机物转化、烷烃/烯烃/芳烃活化、二氧化碳还原、硫化氢分解、水分解产氢气和氧气等。电催化技术主要包含阳极槽、阴极槽、隔膜等，其中阳极槽发生氧化反应，阴极槽发生还原反应，隔膜阻隔了阴阳极电解液并允许质子或氢氧根穿透，实现整个系统的电导性。Renewable resources such as wind, light, water, and tidal heat can be used to produce green electricity. Green electricity can be used for organic matter conversion, alkane/olefin/aromatic activation, carbon dioxide reduction, hydrogen sulfide decomposition, water decomposition to produce hydrogen and oxygen, etc. through electrocatalytic technology. Electrocatalytic technology mainly includes anode tank, cathode tank, diaphragm, etc., in which the anode tank undergoes oxidation reaction, the cathode tank undergoes reduction reaction, and the diaphragm blocks the cathode and cathode electrolytes and allows protons or hydroxides to penetrate, realizing the conductivity of the entire system.
当前的电催化合成是将反应物投入到阳极或阴极电解液中，其在电极或其担载的催化剂表面发生化学反应过程，生成目标产物。对于有机反应物，特别是环状有机物和芳烃，通常易于在电极表面发生聚合、沉积等副反应过程，造成电极有效面积下降，传质受限。此外有机物对隔膜产生溶胀、溶解等有害影响，造成整个电催化反应体系的失效或活性下降，不能稳定、连续运行，致使工业放大应用存在致命的低效率、短寿命等不可克服的难题。另外，当前的电催化合成都是半反应，即仅在阳极或阴极侧发生有机反应，另一侧电极产气，因为隔膜两侧的压力不均衡，实际生产过程了会存在隔膜两侧物质穿透，隔膜寿命短，同样造成系统操作不稳定，同时也浪费了电资源。The current electrocatalytic synthesis is to put the reactants into the anode or cathode electrolyte, and a chemical reaction process occurs on the electrode or the catalyst surface supported by it to generate the target product. For organic reactants, especially cyclic organics and aromatic hydrocarbons, it is usually easy to undergo side reactions such as polymerization and deposition on the electrode surface, resulting in a decrease in the effective area of the electrode and limited mass transfer. In addition, organic matter has harmful effects such as swelling and dissolution on the diaphragm, causing the failure or activity decrease of the entire electrocatalytic reaction system, and it cannot operate stably and continuously, resulting in fatal inefficiency, short life and other insurmountable problems in industrial amplification applications. In addition, the current electrocatalytic synthesis is a half-reaction, that is, the organic reaction occurs only on the anode or cathode side, and the electrode on the other side produces gas. Because the pressure on both sides of the diaphragm is unbalanced, there will be material penetration on both sides of the diaphragm in the actual production process, and the diaphragm life is short, which also causes unstable system operation and wastes electrical resources.
因此为实现电催化过程的大规模工业连续、稳定、高效率的应用，亟需革新当前的电催化反应方式，即避免反应物和/或产物对电极和隔膜的污染、溶胀、覆盖等，同时改变传统的反应方式。亟需开发一种新的电催化有机合成反应技术，实现反应系统的稳定、连续运行，以及工业应用放大。Therefore, in order to realize the large-scale industrial continuous, stable and efficient application of electrocatalytic processes, it is urgent to innovate the current electrocatalytic reaction mode, that is, to avoid the pollution, swelling and covering of electrodes and diaphragms by reactants and/or products, and to change the traditional reaction mode. It is urgent to develop a new electrocatalytic organic synthesis reaction technology to achieve stable and continuous operation of the reaction system and industrial application scale-up.
发明内容Summary of the invention
鉴于此，本发明提供了一种离场电催化反应方法和反应系统，主要目的是解决电催化有机反应的反应物和/产物容易对电极和隔膜产生污染、溶胀、覆盖的技术问题。In view of this, the present invention provides an off-site electrocatalytic reaction method and reaction system, the main purpose of which is to solve the technical problem that reactants and/or products of electrocatalytic organic reactions easily cause contamination, swelling and covering of electrodes and diaphragms.
一方面，本发明提供了一种离场电催化反应方法，所述方法包括以下步骤：In one aspect, the present invention provides a method for an off-site electrocatalytic reaction, the method comprising the following steps:
所述离场电催化反应方法包括以下步骤：The off-site electrocatalytic reaction method comprises the following steps:
电池系统中电解液离子对与电极进行电子交换反应，获得氧化电势或还原电势；获得氧化电势或还原电势的电解液进入电池系统外部的独立反应系统，与所述反应系统中的反应物进行氧化还原反应，得到含反应产物的混合物，经分离后，经过所述氧化还原反应后的电解液返回至所述电池系统再次获得氧化电势或还原电势。The electrolyte ions in the battery system undergo an electron exchange reaction with the electrodes to obtain an oxidation potential or a reduction potential; the electrolyte having obtained the oxidation potential or the reduction potential enters an independent reaction system outside the battery system, undergoes an oxidation-reduction reaction with the reactants in the reaction system, and obtains a mixture containing reaction products; after separation, the electrolyte after the oxidation-reduction reaction is returned to the battery system to obtain the oxidation potential or the reduction potential again.
本发明中的电池系统与反应系统为独立系统，两者之间可通过管道连接，管道用于电解液在电池系统与反应系统之间流动。The battery system and the reaction system in the present invention are independent systems, and the two can be connected by a pipeline, and the pipeline is used for the electrolyte to flow between the battery system and the reaction system.
本发明中电解液是电池系统通电后与电极发生电子交换反应以获得氧化电势或还原电势。The electrolyte in the present invention is the electrolyte that undergoes electron exchange reaction with the electrode after the battery system is powered on to obtain oxidation potential or reduction potential.
本发明的上述离场式电催化反应方法是将传统的在电解池中进行反应物化学反应移动到电解池外另一个反应场所中进行反应，只需要电解液在电解池与反应场所之间循环输送即可，这样可避免传统技术中反应物的化学反应在电解池中进行而对电极或隔膜产生污染、溶胀、覆盖的问题。The above-mentioned off-site electrocatalytic reaction method of the present invention is to move the traditional chemical reaction of reactants in the electrolytic cell to another reaction site outside the electrolytic cell for reaction. It only needs to circulate the electrolyte between the electrolytic cell and the reaction site. This can avoid the problem of contamination, swelling and covering of electrodes or diaphragms caused by the chemical reaction of reactants in the electrolytic cell in the traditional technology.
本发明的上述离场电催化方法可适用于以下五种反应方式：The above-mentioned off-site electrocatalytic method of the present invention can be applied to the following five reaction modes:
第一种：阳极电解池与氧化反应系统连通，单独进行氧化反应。The first type: the anode electrolytic cell is connected to the oxidation reaction system and the oxidation reaction is carried out alone.
第二种：阴极电解池与还原反应系统连通，单独进行还原反应。The second type: the cathode electrolytic cell is connected to the reduction reaction system and the reduction reaction is carried out alone.
第三种：阳极电解池与氧化反应系统连通，单独进行氧化反应，同时，阴极电解池与还原反应系统连通，单独进行还原反应；氧化反应系统和还原反应系统各自独立的进行化学反应；即并联方式；The third type: the anode electrolytic cell is connected to the oxidation reaction system and performs oxidation reaction alone, while the cathode electrolytic cell is connected to the reduction reaction system and performs reduction reaction alone; the oxidation reaction system and the reduction reaction system perform chemical reactions independently; i.e., the parallel mode;
第四种：阳极电解池与氧化反应系统连通进行氧化反应，阴极电解池与还原反应系统连通进行还原反应，特别的，氧化反应的产物进入还原反应系统作为反应物继续和阴极电解液进行还原反应，形成氧化反应系统-还原反应系统2级串联反应系统。The fourth type: the anode electrolytic cell is connected to the oxidation reaction system for oxidation reaction, and the cathode electrolytic cell is connected to the reduction reaction system for reduction reaction. In particular, the product of the oxidation reaction enters the reduction reaction system as a reactant to continue to react with the cathode electrolyte to form oxygen. Chemical reaction system-reduction reaction system two-stage series reaction system.
第五种：在第四种方式的基础上，再增加一组电解池和氧化反应系统，形成氧化反应系统-还原反应系统-氧化反应系统3级串联反应系统。The fifth method: On the basis of the fourth method, another set of electrolytic cells and oxidation reaction systems are added to form a three-stage series reaction system of oxidation reaction system-reduction reaction system-oxidation reaction system.
本发明的离场式电催化反应液可以在上述物种连接方式之外，根据实际反应过程，将氧化、还原过程在电解池外进行多级串联或并联组合。In addition to the above-mentioned species connection method, the off-site electrocatalytic reaction liquid of the present invention can carry out oxidation and reduction processes in multiple stages of series or parallel combination outside the electrolytic cell according to the actual reaction process.
可选地，所述电池系统的阳极电解池中具有氧化还原性的阳极电解液Mx+在阳极表面发生氧化反应，形成具有氧化电势的氧化电解液M(x+1)+；Optionally, the anolyte Mx+ with redox properties in the anolyte cell of the battery system undergoes an oxidation reaction on the anode surface to form an oxidizing electrolyte M(x+1)+ with an oxidation potential;
所述氧化电解液M(x+1)+进入氧化反应系统，与所述氧化反应系统中的反应物I发生氧化反应，所述反应物I经过氧化后得到反应产物I，所述氧化电解液M(x+1)+被还原，得到阳极电解液Mx+，经分离后，所述阳极电解液Mx+返回至所述阳极电解池中，再次与阳极反应，形成具有氧化电势的氧化电解液M(x+1)+；The oxidizing electrolyte M(x+1)+ enters the oxidation reaction system, undergoes an oxidation reaction with the reactant I in the oxidation reaction system, and the reactant I is oxidized to obtain a reaction product I. The oxidizing electrolyte M(x+1)+ is reduced to obtain an anolyte Mx+ . After separation, the anolyte Mx+ is returned to the anolyte cell and reacts with the anode again to form an oxidizing electrolyte M(x+1)+ having an oxidation potential;
所述电池系统中的阴极电解液在阴极电解池内进行氧化还原反应。The cathode electrolyte in the battery system undergoes a redox reaction in the cathode electrolytic cell.
本发明的上述过程为电解池外的阳极半反应过程；Mx+、M(x+1)+中的x为M离子的价态。The above process of the present invention is an anode half-reaction process outside the electrolytic cell; x in Mx+ , M(x+1)+ is the valence state of the M ion.
可选地，所述电池系统的阴极电解池中具有氧化还原性的阴极电解液Ny+在阴极表面发生还原反应，形成具有还原电势的还原电解液N(y-1)+；Optionally, the cathode electrolyte Ny+ with redox properties in the cathode electrolytic cell of the battery system undergoes a reduction reaction on the cathode surface to form a reducing electrolyte N(y-1)+ with a reduction potential;
所述还原电解液N(y-1)+进入还原反应系统，与所述还原反应系统中的反应物II发生还原反应，所述反应物II经过还原后得到反应产物II，所述还原电解液N(y-1)+被氧化，得到阴极电解液Ny+，经分离后，所述阴极电解液Ny+返回至所述阴极电解池中，再次与阴极反应，形成具有还原电势的还原电解液N(y-1)+；The reducing electrolyte N(y-1)+ enters the reduction reaction system, undergoes a reduction reaction with the reactant II in the reduction reaction system, and the reactant II is reduced to obtain a reaction product II. The reducing electrolyte N(y-1)+ is oxidized to obtain a cathode electrolyte Ny+ . After separation, the cathode electrolyte Ny+ is returned to the cathode electrolytic cell and reacts with the cathode again to form a reducing electrolyte N(y-1)+ having a reduction potential.
所述电池系统中的阳极电解液在阳极电解池内进行氧化还原反应。The anolyte in the battery system undergoes a redox reaction in the anolyte cell.
本发明的上述过程为电解池外的阴极半反应过程；Ny+、N(y-1)+中的y为N离子的价态。The above process of the present invention is a cathode half-reaction process outside the electrolytic cell; y in Ny+ and N(y-1)+ is the valence state of the N ion.
可选地，所述电池系统的阳极电解池中具有氧化还原性的阳极电解液Mx+在阳极表面发生氧化反应，形成具有氧化电势的氧化电解液M(x+1)+I；Optionally, the anolyte Mx+ with redox properties in the anolyte cell of the battery system undergoes an oxidation reaction on the anode surface to form an oxidizing electrolyte M(x+1)+ I with an oxidation potential;
所述氧化电解液M(x+1)+I进入氧化反应系统I，与所述氧化反应系统I中的反应物I发生氧化反应I，所述反应物I经过氧化后得到反应产物I，所述氧化电解液M(x+1)+I被还原，得到阳极电解液Mx+，经分离后，所述阳极电解液Mx+返回至所述阳极电解池中，再次与阳极反应，形成具有氧化电势的氧化电解液M(x+1)+；循环氧化-还原过程；The oxidizing electrolyte M(x+1)+ I enters the oxidation reaction system I, and undergoes an oxidation reaction I with the reactant I in the oxidation reaction system I. The reactant I is oxidized to obtain a reaction product I. The oxidizing electrolyte M(x+1)+ I is reduced to obtain an anolyte Mx+ . After separation, the anolyte Mx+ is returned to the anolyte cell and reacts with the anode again to form an oxidizing electrolyte M(x+1)+ with an oxidation potential; a cyclic oxidation-reduction process;
所述电池系统的阴极电解池中具有氧化还原性的阴极电解液Ny+在阴极表面发生还原反应，形成具有还原电势的还原电解液N(y-1)+I；The cathode electrolyte Ny+ with redox properties in the cathode electrolytic cell of the battery system undergoes a reduction reaction on the cathode surface to form a reducing electrolyte N(y-1)+ I with a reduction potential;
所述还原电解液N(y-1)+I进入还原反应系统I，与所述还原反应系统I的反应物II发生还原反应I，所述反应物II经过还原后得到反应产物II，所述还原电解液N(y-1)+I被氧化，得到阴极电解液Ny+，经分离后，所述阴极电解液Ny+返回至所述阴极电解池中，再次与阴极反应，形成具有还原电势的还原电解液N(y-1)+；循环还原-氧化过程。The reducing electrolyte N(y-1)+ I enters the reduction reaction system I, and undergoes a reduction reaction I with the reactant II of the reduction reaction system I. After reduction, the reactant II obtains a reaction product II. The reducing electrolyte N(y-1)+ I is oxidized to obtain a cathode electrolyte Ny+ . After separation, the cathode electrolyte Ny+ is returned to the cathode electrolytic cell and reacts with the cathode again to form a reducing electrolyte N(y-1)+ with a reduction potential; a cyclic reduction-oxidation process.
本发明上述过程中，阳极电解液在阳极电解池与氧化反应系统之间循环经历被还原-被氧化-再还原-再氧化等的过程，反应物在氧化反应系统内进行氧化反应；独立的，阴极电解液在阴极电解池与还原反应系统之间循环进行被氧化-被还原-再氧化-再还原的过程，反应物在还原反应系统内进行还原反应。In the above process of the present invention, the anolyte circulates between the anolyte cell and the oxidation reaction system to undergo a process of reduction-oxidation-re-reduction-reoxidation, and the reactants undergo an oxidation reaction in the oxidation reaction system; independently, the catholyte circulates between the catholyte cell and the reduction reaction system to undergo a process of oxidation-reduction-reoxidation-reduction, and the reactants undergo a reduction reaction in the reduction reaction system.
本发明的上述离场电催化技术中，先用电解池系统，通过电解的方法制备具有氧化势能的媒介体、具有还原势能的媒介体；随后将具有氧化势能的媒介体通入到氧化反应器中，在催化剂作用下，与反应物间发生氧化反应；将具有还原势能的媒介体通入到还原反应器中，在催化剂作用下，与反应物间发生还原反应。In the above-mentioned off-site electrocatalytic technology of the present invention, an electrolytic cell system is first used to prepare a medium with oxidation potential and a medium with reduction potential by an electrolytic method; then the medium with oxidation potential is introduced into an oxidation reactor, and an oxidation reaction occurs between the medium and the reactants under the action of a catalyst; and the medium with reduction potential is introduced into a reduction reactor, and a reduction reaction occurs between the medium and the reactants under the action of a catalyst.
可选地，所述氧化反应系统I的所述反应产物I进入所述还原反应系统I内，作为所述还原反应系统I的反应物II和所述还原反应系统I内的所述还原电解液N(y-1)+I进行还原反应I，得到所述反应产物II。Optionally, the reaction product I of the oxidation reaction system I enters the reduction reaction system I, acts as the reactant II of the reduction reaction system I and the reducing electrolyte N(y-1)+ I in the reduction reaction system I to carry out reduction reaction I to obtain the reaction product II.
本发明上述过程中，将氧化反应系统和还原反应系统串联起来，即将氧化反应的产物作为还原反应系统的反应物继续反应。In the above process of the present invention, the oxidation reaction system and the reduction reaction system are connected in series, that is, the product of the oxidation reaction is used as the reactant of the reduction reaction system to continue the reaction.
可选地，所述还原反应系统I的所述反应产物II进入所述氧化反应系统I，作为所述氧化反应系统I的反应物III，与所述氧化反应系统I中的所述氧化电解液M(x+1)+I进行氧化反应II，得到所述反应产物III。Optionally, the reaction product II of the reduction reaction system I enters the oxidation reaction system I as the reactant III of the oxidation reaction system I, and undergoes oxidation reaction II with the oxidizing electrolyte M(x+1)+ I in the oxidation reaction system I to obtain the reaction product III.
本发明上述过程中，当第一步氧化反应I进行较快时，可将还原反应系统I的出口和氧化反应系统I的入口连通起来，反应物II在氧化反应系统I中与所述氧化电解液M(x+1)+I继续进行第二次氧化反应，得到反应产物III，该过程为闭环反应，In the above process of the present invention, when the first oxidation reaction I proceeds faster, the outlet of the reduction reaction system I and the inlet of the oxidation reaction system I can be connected, and the reactant II continues to undergo a second oxidation reaction with the oxidation electrolyte M(x+1) + I in the oxidation reaction system I to obtain a reaction product III. This process is a closed-loop reaction.
可选地，所述还原反应系统I的所述反应产物II进入氧化反应系统II，作为所述氧化反应系统II的反应物III，与所述氧化反应系统II中的氧化电解液M(x+1)+II进行氧化反应II，得到所述反应产物III。Optionally, the reaction product II of the reduction reaction system I enters the oxidation reaction system II, serves as the reactant III of the oxidation reaction system II, and undergoes oxidation reaction II with the oxidizing electrolyte M(x+1)+ II in the oxidation reaction system II to obtain the reaction product III.
本发明上述过程中，当第一步氧化反应I进程较慢，后续流程持续进行时，可以在还原反应系统I后面连通新的氧化反应系统II，同时连接新的电池系统II，还原反应系统的反应物II在新的氧化反应系统II中与新的电池系统中的新氧化电解液M(x+1)+II进行第二次氧化反应，得到反应产物III，该过程为开环反应。In the above process of the present invention, when the first step oxidation reaction I progresses slowly and the subsequent process continues, a new oxidation reaction system II can be connected behind the reduction reaction system I, and a new battery system II is connected at the same time. The reactant II of the reduction reaction system undergoes a second oxidation reaction in the new oxidation reaction system II with the new oxidation electrolyte M(x+1)+ II in the new battery system to obtain a reaction product III. This process is a ring-opening reaction.
本发明的上述过程中，将氧化反应系统、还原反应系统、氧化反应系统多级串联，用于匹配性的实现具有氧化、还原、氧化的化学反应过程。In the above process of the present invention, the oxidation reaction system, the reduction reaction system and the oxidation reaction system are connected in series in multiple stages to match and realize the chemical reaction process of oxidation, reduction and oxidation.
可选地，所述电解液的溶质包括氧化还原离子对；所述氧化还原离子对选自无机金属离子对、有机金属离子对、有机对以及无机对中的至少一种。Optionally, the solute of the electrolyte includes a redox ion pair; the redox ion pair is selected from at least one of an inorganic metal ion pair, an organic metal ion pair, an organic pair and an inorganic pair.
可选地，所述电解液的溶剂包括酸或碱的水溶液、有机溶液以及水与有机物复合溶剂中的至少一种；Optionally, the solvent of the electrolyte includes at least one of an acid or alkali aqueous solution, an organic solution, and a composite solvent of water and organic matter;
所述酸选自无机酸和/或有机酸；The acid is selected from inorganic acids and/or organic acids;
所述酸的浓度为0.01～6mol/L；The concentration of the acid is 0.01 to 6 mol/L;
优选地，酸总浓度为0.01～3摩尔/升。Preferably, the total acid concentration is 0.01 to 3 mol/L.
所述无机酸选自H2SO4、HCl、H3PO4和HClO4中的至少一种；The inorganic acid is selected from at least one of H2 SO4 , HCl, H3 PO4 and HClO4 ;
所述有机酸选自乙酸、三氟乙酸和苯磺酸中的至少一种；The organic acid is selected from at least one of acetic acid, trifluoroacetic acid and benzenesulfonic acid;
所述有机溶液选自甲醇、甲醚、乙腈、乙酸乙酯、氯仿、二氯甲烷以及二甲基亚砜中的至少一种。The organic solvent is selected from at least one of methanol, dimethyl ether, acetonitrile, ethyl acetate, chloroform, dichloromethane and dimethyl sulfoxide.
所述电解液可以添加碱金属等增加电解液的导电性和优化催化活性，但不仅限于上述金属无机盐；The electrolyte may be added with alkali metals and the like to increase the conductivity of the electrolyte and optimize the catalytic activity, but is not limited to the above-mentioned metal inorganic salts;
可选地，所述阳极电解池中的阳极电解液的溶质包括氧化还原离子对I，所述氧化还原离子对I选自I3-/I-、Br2/Br-、Fe(III)/Fe(II)、[Fe(CN)6]3-/[Fe(CN)6]4-、VO2(I)/VO(II)、Ce(IV)/Ce(III)以及K2MnO4/KMnO4中的至少一种。Optionally, the solute of the anolyte in the anolyte cell comprises a redox ion pair I, and the redox ion pair I is selected from at least one of I3− /I− , Br2 /Br− , Fe(III)/Fe(II), [Fe(CN)6 ]3- /[Fe(CN)6 ]4- , VO2 (I)/VO(II), Ce(IV)/Ce(III) and K2 MnO4 /KMnO4 .
可选地，所述阴极电解池中的阴极电解液的溶质包括氧化还原离子对II，所述氧化还原离子对II选自无机金属离子对、有机金属离子对、有机对、无机对中的至少一种；Optionally, the solute of the cathode electrolyte in the cathode electrolytic cell comprises a redox ion pair II, and the redox ion pair II is selected from at least one of an inorganic metal ion pair, an organic metal ion pair, an organic pair, and an inorganic pair;
所述无机金属离子对选自Eu(II)/Eu(III)、Cr(II)/Cr(III)和V(II)/V(III)中的至少一种；The inorganic metal ion pair is selected from at least one of Eu(II)/Eu(III), Cr(II)/Cr(III) and V(II)/V(III);
所述有机金属离子对选自有机物配位钴(II)/有机物配位钴(III)、三乙醇胺铁(II)/三乙醇胺铁(III)等中的至少一种；The organic metal ion pair is selected from at least one of organic-coordinated cobalt (II)/organic-coordinated cobalt (III), triethanolamine iron (II)/triethanolamine iron (III), etc.;
所述有机对选自醌/酚有机对；优选苯二醌/对苯二酚、二苯甲酮/二苯甲醇中的至少一种；The organic pair is selected from quinone/phenol organic pairs; preferably at least one of benzoquinone/hydroquinone, benzophenone/benzhydrol;
所述无机对选自杂多酸。The inorganic pair is selected from heteropoly acids.
可选地，所述有机物配位钴(II)/有机物配位钴(III)选自卟啉钴(II)/卟啉钴(III)；Optionally, the organic-coordinated cobalt (II)/organic-coordinated cobalt (III) is selected from porphyrin cobalt (II)/porphyrin cobalt (III);
本发明的上述阳极电解液中的离子对适用于和有机物进行氧化反应；该有机物可选自含氧有机物、含氮有机物，烷烃、芳烃、烯烃、炔烃、H2O、CO、H2S中的至少一种。The ion pairs in the anode electrolyte of the present invention are suitable for oxidation reaction with organic matter; the organic matter can be selected from at least one of oxygen-containing organic matter, nitrogen-containing organic matter, alkanes, aromatic hydrocarbons, alkenes, alkynes,H2O , CO, andH2S .
本发明的上述阴极电解液中的离子对适用于和有机物进行还原反应；该有机物可选自含氧有机物、含氮有机物、氮氧化合物、烯烃、炔烃、芳烃、质子、CO2、CO、氮气中的至少一种。The ion pairs in the cathode electrolyte of the present invention are suitable for reduction reaction with organic matter; the organic matter can be selected from at least one of oxygen-containing organic matter, nitrogen-containing organic matter, nitrogen oxides, olefins, alkynes, aromatic hydrocarbons, protons, CO2 , CO, and nitrogen.
可选地，所述反应物包括苯，所述反应产物包括己二酸。Optionally, the reactant comprises benzene and the reaction product comprises adipic acid.
可选地，所述氧化反应系统I的反应物I包括苯，反应产物I包括苯酚；所述还原反应系统I的反应物II包括所述苯酚，所述反应产物II包括环己酮。Optionally, the reactant I of the oxidation reaction system I includes benzene, and the reaction product I includes phenol; the reactant II of the reduction reaction system I includes the phenol, and the reaction product II includes cyclohexanone.
可选地，所述反应物III包括环己酮，所述反应产物III包括己二酸。Optionally, the reactant III includes cyclohexanone, and the reaction product III includes adipic acid.
第二方面，本发明提供了一种用于上述离场电催化反应方法中的电催化反应装置，包括：In a second aspect, the present invention provides an electrocatalytic reaction device for use in the above-mentioned off-site electrocatalytic reaction method, comprising:
电池系统，其用于提供具有氧化还原性的电解液；A battery system for providing an electrolyte having redox properties;
反应系统，其用于为所述电池系统送出的电解液和反应系统中的反应物进行氧化还原反应提供反应空间；A reaction system, which is used to provide a reaction space for the electrolyte delivered by the battery system and the reactants in the reaction system to undergo a redox reaction;
分离系统，其用于分离反应产物与经过氧化还原反应后的电解液；A separation system, which is used to separate the reaction product from the electrolyte after the redox reaction;
所述电池系统的出液口和所述反应系统的入口连通；The liquid outlet of the battery system is in communication with the inlet of the reaction system;
所述反应系统的出口和所述分离系统的入口连通；The outlet of the reaction system is connected to the inlet of the separation system;
所述分离系统的电解液出口和所述电池系统的入液口连通，所述分离系统具有产物出口。The electrolyte outlet of the separation system is communicated with the liquid inlet of the battery system, and the separation system has a product outlet.
本发明的电池系统由阳极槽、阴极槽、隔膜等三部分组成，其中阴极室和阳极室由离子交换膜隔开避免阴阳极电解液交叉或穿透污染。阴极和阳极电解液是酸性的水和/或有机物复合物。阳极的溶质是具有氧化还原性的媒介体Mx+，其在阳极表面发生氧化反应，价态升高，此时获得氧化电势M(x+1)+；阴极的溶质是具有氧化还原性的媒介体Ny+，其在阴极表面发生还原反应，价态降低，此时获得具有还原电势N(y-1)+。The battery system of the present invention is composed of three parts, namely, an anode tank, a cathode tank, and a diaphragm, wherein the cathode chamber and the anode chamber are separated by an ion exchange membrane to prevent cross or penetration contamination of the cathode and anode electrolytes. The cathode and anode electrolytes are acidic water and/or organic compounds. The solute of the anode is a redox mediator Mx+ , which undergoes an oxidation reaction on the anode surface, and the valence state increases, and an oxidation potential M(x+1)+ is obtained at this time; the solute of the cathode is a redox mediator Ny+ , which undergoes a reduction reaction on the cathode surface, and the valence state decreases, and a reduction potential N(y-1)+ is obtained at this time.
将获得氧化电势的M(x+1)+通入另一个反应器中，与反应物发生氧化反应，媒介体被还原生成Mx+，将媒介体和反应物/产物分离，随后媒介体再回到阳极槽，完成阳极侧的电化学/催化反应。在另一个空间分离的反应器中，还原的媒介体N(y-1)+与反应物发生还原反应，媒介体被氧化生成Ny+，将媒介体和反应物/产物分离，随后媒介体再回到阴极槽，完成阴极侧的电化学/催化反应。The M(x+1)+ with oxidation potential is introduced into another reactor to undergo oxidation reaction with the reactant, the mediator is reduced to generate Mx+ , the mediator and the reactant/product are separated, and then the mediator returns to the anode tank to complete the electrochemical/catalytic reaction on the anode side. In the reactor with separation between the cathode and the reactant, the reduced mediator N(y-1) + undergoes a reduction reaction with the reactant, the mediator is oxidized to generate Ny+ , the mediator and the reactant/product are separated, and then the mediator returns to the cathode tank to complete the electrochemical/catalytic reaction on the cathode side.
特别地，对于“离场”电催化串联反应技术，还原反应器的反应物是氧化反应器的产物，该产物也可以再次进入氧化反应器发生氧化反应。In particular, for the "off-site" electrocatalytic series reaction technology, the reactant of the reduction reactor is the product of the oxidation reactor, and the product can also enter the oxidation reactor again to undergo oxidation reaction.
可选地，所述电池系统包含H型电解池、液流电池或无电解液的隔膜流动电解池。Optionally, the battery system comprises an H-type electrolytic cell, a liquid flow battery, or an electrolyte-free diaphragm flow electrolytic cell.
可选地，所述液流电池包括阳极电解池和阴极电解池，其阳极和阴极各自独立的选自碳棒、碳毡、钛网和铜网中的至少一种。Optionally, the liquid flow battery comprises an anode electrolytic cell and a cathode electrolytic cell, wherein the anode and cathode are independently selected from at least one of a carbon rod, a carbon felt, a titanium mesh and a copper mesh.
可选地，所述阳极和阴极的表面各自独立的沉积Pt、Pd、Bi、Ag、Pb金属中的至少一种。Optionally, at least one of Pt, Pd, Bi, Ag, and Pb metals is independently deposited on the surfaces of the anode and the cathode.
本发明的碳棒、碳毡、钛网和铜网可直接用作阳极或阴极，也可以在其表面沉积上述金属。The carbon rod, carbon felt, titanium mesh and copper mesh of the present invention can be directly used as anode or cathode, or the above metals can be deposited on their surfaces.
可选地，所述反应系统包括氧化反应器和/或还原反应器；所述分离系统包括萃取器和精馏塔；所述萃取器的产物出口与所述精馏塔的入口连通，所述精馏塔具有产物出口。Optionally, the reaction system includes an oxidation reactor and/or a reduction reactor; the separation system includes an extractor and a distillation tower; the product outlet of the extractor is connected to the inlet of the distillation tower, and the distillation tower has a product outlet.
可选地，所述阳极电解池的出液口与所述氧化反应器的入口连通，所述氧化反应器中设置反应物，所述氧化反应器的出口与所述萃取器的入口连通，所述萃取器的产物出口与所述精馏塔的入口连通，所述萃取器的电解液出口与所述阳极电解池的入液口连通，所述精馏塔具有产物出口。Optionally, the liquid outlet of the anode electrolytic cell is connected to the inlet of the oxidation reactor, reactants are arranged in the oxidation reactor, the outlet of the oxidation reactor is connected to the inlet of the extractor, the product outlet of the extractor is connected to the inlet of the distillation tower, the electrolyte outlet of the extractor is connected to the liquid inlet of the anode electrolytic cell, and the distillation tower has a product outlet.
可选地，所述阴极电解池的出液口与所述还原反应器的入口连通，所述还原反应器中设置反应物，所述还原反应器的出口与所述萃取器的入口连通，所述萃取器的产物出口与所述精馏塔的入口连通，所述萃取器的电解液出口与所述阴极电解池的入液口连通，所述精馏塔具有产物出口。Optionally, the liquid outlet of the cathode electrolytic cell is connected to the inlet of the reduction reactor, reactants are arranged in the reduction reactor, the outlet of the reduction reactor is connected to the inlet of the extractor, the product outlet of the extractor is connected to the inlet of the distillation tower, the electrolyte outlet of the extractor is connected to the liquid inlet of the cathode electrolytic cell, and the distillation tower has a product outlet.
可选地，所述阳极电解池I的出液口与所述氧化反应器I的入口连通，所述氧化反应器I中设置反应物，所述氧化反应器I的出口与萃取器I的入口连通，所述萃取器I的产物出口与精馏塔I的入口连通，所述萃取器I的电解液出口与所述阳极电解池I的入液口连通；所述精馏塔I的产物I出口与所述还原反应器的入口连通，所述阴极电解池的出液口与所述还原反应器的入口连通，所述还原反应器的出口与萃取器II的入口连通，所述萃取器II的产物出口与精馏塔II的入口连通，所述萃取器II的电解液出口与所述阴极电解池的入液口连通，所述精馏塔II具有产物II出口。Optionally, the liquid outlet of the anode electrolytic cell I is connected to the inlet of the oxidation reactor I, a reactant is arranged in the oxidation reactor I, the outlet of the oxidation reactor I is connected to the inlet of the extractor I, and the product outlet of the extractor I is connected to the inlet of the distillation tower I. The electrolyte outlet of the extractor I is connected to the liquid inlet of the anode electrolytic cell I; the product I outlet of the distillation tower I is connected to the inlet of the reduction reactor, the liquid outlet of the cathode electrolytic cell is connected to the inlet of the reduction reactor, the outlet of the reduction reactor is connected to the inlet of the extractor II, the product outlet of the extractor II is connected to the inlet of the distillation tower II, the electrolyte outlet of the extractor II is connected to the liquid inlet of the cathode electrolytic cell, and the distillation tower II has a product II outlet.
可选地，所述精馏塔II的产物II出口与所述氧化反应器I的入口连通；Optionally, the product II outlet of the distillation tower II is connected to the inlet of the oxidation reactor I;
或者，所述精馏塔II的产物II出口与氧化反应器II的入口连通，阳极电解池II的出液口与所述氧化反应器II的入口连通；所述氧化反应器II的出口与萃取器III的入口连通，所述萃取器III的产物出口与精馏塔III的入口连通，所述萃取器III的电解液出口与所述阳极电解池II的入液口连通，所述精馏塔III具有产物III出口。Alternatively, the product II outlet of the distillation tower II is connected to the inlet of the oxidation reactor II, and the liquid outlet of the anode electrolysis cell II is connected to the inlet of the oxidation reactor II; the outlet of the oxidation reactor II is connected to the inlet of the extractor III, the product outlet of the extractor III is connected to the inlet of the distillation tower III, the electrolyte outlet of the extractor III is connected to the liquid inlet of the anode electrolysis cell II, and the distillation tower III has a product III outlet.
本发明的上述电催化反应方法和电催化反应系统可用于苯制苯酚、苯酚制环己酮、环己酮制己二酸或者苯制己二酸。The electrocatalytic reaction method and electrocatalytic reaction system of the present invention can be used for preparing phenol from benzene, preparing cyclohexanone from phenol, preparing adipic acid from cyclohexanone or preparing adipic acid from benzene.
可选地，所述的电池系统的温度为5～80℃，压力是1～30bar。Optionally, the temperature of the battery system is 5 to 80° C., and the pressure is 1 to 30 bar.
可选地，所述氧化反应器选自固定床、槽式反应器、浆态床、塔板反应器或流化床反应器；氧化反应器的压力为1～200bar，温度为5～200℃。Optionally, the oxidation reactor is selected from a fixed bed, a tank reactor, a slurry bed, a tray reactor or a fluidized bed reactor; the pressure of the oxidation reactor is 1 to 200 bar, and the temperature is 5 to 200°C.
优选地，所述氧化反应器的压力为1～20bar，温度为15～50℃。Preferably, the pressure of the oxidation reactor is 1-20 bar and the temperature is 15-50°C.
可选地，所述氧化反应器中可以不使用催化剂或可选择性的放置催化剂I，所述催化剂I的活性组分选自Au、Cu、Ru、Ir、Pt、Pd、Rh、Fe、Co金属及其氧化物中的至少一种；所述催化剂I可以是负载型的，也可以是金属颗粒直接使用。Optionally, no catalyst may be used in the oxidation reactor or catalyst I may be selectively placed, and the active component of the catalyst I is selected from at least one of Au, Cu, Ru, Ir, Pt, Pd, Rh, Fe, Co metals and their oxides; the catalyst I may be a supported type or may be directly used as metal particles.
可选地，催化剂可以直接是碳化物、磷化物、氮化物等中的至少一种。Alternatively, the catalyst may be directly at least one of carbide, phosphide, nitride and the like.
可选地，所述氧化反应器中的反应物选自含氧有机物、含氮有机物，烷烃、芳烃、烯烃、炔烃、H2O、CO、H2S中的至少一种。Optionally, the reactant in the oxidation reactor is selected from at least one of oxygen-containing organic matter, nitrogen-containing organic matter, alkanes, aromatic hydrocarbons, alkenes, alkynes, H2 O, CO, and H2 S.
可选地，所述还原反应器选自固定床、槽式反应器、浆态床反应器或流化床反应器；所述还原反应器的压力为1～200bar，温度为5～200℃。Optionally, the reduction reactor is selected from a fixed bed, a tank reactor, a slurry bed reactor or a fluidized bed reactor; the pressure of the reduction reactor is 1 to 200 bar, and the temperature is 5～200℃.
优选地，还原反应器的压力为1～20bar，温度为15～50℃。Preferably, the pressure of the reduction reactor is 1-20 bar and the temperature is 15-50°C.
可选地，所述还原反应器中可不使用催化剂或可选择性的放置催化剂II，所述催化剂II的活性组分选自Au、Cu、Ru、Ir、Pt、Pd、Rh、Fe、Co金属及其氧化物中的至少一种。所述催化剂I可以是负载型的，也可以是金属颗粒直接使用。Optionally, no catalyst may be used in the reduction reactor or a catalyst II may be selectively placed, wherein the active component of the catalyst II is selected from at least one of Au, Cu, Ru, Ir, Pt, Pd, Rh, Fe, Co metals and their oxides. The catalyst I may be a supported type or may be directly used as metal particles.
可选地，催化剂可以直接是碳化物、磷化物、氮化物等中的至少一种。Alternatively, the catalyst may be directly at least one of carbide, phosphide, nitride and the like.
可选地，所述还原反应器中的反应物选自含氧有机物、含氮有机物、氮氧化合物、烯烃、炔烃、芳烃、质子、CO2、CO、氮气中的至少一种。Optionally, the reactant in the reduction reactor is selected from at least one of oxygen-containing organic matter, nitrogen-containing organic matter, nitrogen oxides, olefins, alkynes, aromatic hydrocarbons, protons, CO2 , CO, and nitrogen.
本发明的整个电催化系统包含电池系统、氧化反应器、还原反应器、萃取器和精馏塔等。氧化反应器和还原反应器的产物和氧化还原媒介体通过有机溶剂萃取分离，回到阳极槽和阴极槽的氧化还原媒介体不含有反应物和产物，避免了对电极、隔膜等的污染。这种将反应物和产物与电极和隔膜分离，且将氧化反应器和还原反应器串联在一起的操作方法，就是本发明提出的新的电催化反应技术，称之为“离场”电催化串联反应技术。这个“离场”电催化反应系统不仅在基础研究的实验室方面可以进行基础理论研究，而且电池放大不需要因为放大效应而引起的对流道、内部结构工艺的调整，氧化和还原反应器在工业上非常成熟，易于放大，因此也可以进行电化学示范、中试、应用等尺度下的工业测试。The entire electrocatalytic system of the present invention comprises a battery system, an oxidation reactor, a reduction reactor, an extractor and a distillation tower, etc. The products and redox media of the oxidation reactor and the reduction reactor are separated by organic solvent extraction, and the redox media returned to the anode tank and the cathode tank do not contain reactants and products, thereby avoiding contamination of electrodes, diaphragms, etc. This operation method of separating reactants and products from electrodes and diaphragms and connecting the oxidation reactor and the reduction reactor in series is the new electrocatalytic reaction technology proposed by the present invention, which is called "off-site" electrocatalytic series reaction technology. This "off-site" electrocatalytic reaction system can not only conduct basic theoretical research in the laboratory of basic research, but also the battery amplification does not require the adjustment of the flow channel and the internal structure process caused by the amplification effect. The oxidation and reduction reactors are very mature in industry and easy to amplify, so industrial tests at the scale of electrochemical demonstration, pilot test, and application can also be carried out.
优选地，以苯制己二酸为例，分步的反应过程如下：Preferably, taking benzene to adipic acid as an example, the step-by-step reaction process is as follows:
阳极槽：Mx+-e-→M(x+1)+ (1)Anode tank: Mx+ -e- →M(x+1)+ (1)
阴极槽：Ny++e-→N(y-1)+ (2)Cathode tank: Ny+ +e- →N(y-1)+ (2)
氧化反应器：苯+M(x+1)++H2O→苯酚+Mx++2H+ (3)Oxidation reactor: benzene + M(x+1) + +H2 O → phenol + Mx + +2H+ (3)
还原反应器：苯酚+4N(y-1)++4H+→环己酮+4Ny+ (4)Reduction reactor: phenol + 4N(y-1) + + 4H+ → cyclohexanone + 4Ny + (4)
氧化反应器：环己酮+M(x+1)++2H2O→己二酸+Mx++2H+ (5)Oxidation reactor: Cyclohexanone + M(x+1) + +2H2 O → Adipic acid + Mx + +2H+ (5)
总反应：苯+4H2O→己二酸+2H2 (6)Overall reaction: benzene + 4H2 O → adipic acid + 2H2 (6)
本发明离场电催化技术除了可应用于进行苯制己二酸串联反应外，氧化反应器和还原反应器也可以单独使用。例如氧化反应器进行氧化反应，还原反应器进行放氢实验；反之，还原反应器进行还原反应，氧化反应器进行放氧实验。所述氧化反应器的反应物可以选自含氧有机物、含氮有机物，烷烃、芳烃、烯烃、炔烃、H2O、CO、H2S等中的至少一种，但不仅限于这些物质；所述还原反应器中的反应物可以选自含氧有机物、含氮有机物、氮氧化合物、烯烃、炔烃、芳烃、质子、CO2、CO、氮气等中的至少一种，但不仅限于这些物质。此外，当氧化反应器使用H2O，还原反应器使用质子时，氧化反应器产生氧气，还原反应器产生氢气，就是双离场的水分解过程。In addition to being applicable to the series reaction of benzene to adipic acid, the off-site electrocatalytic technology of the present invention can also be used separately in the oxidation reactor and the reduction reactor. For example, the oxidation reactor performs an oxidation reaction, and the reduction reactor performs a hydrogen release experiment; conversely, the reduction reactor performs a reduction reaction, and the oxidation reactor performs an oxygen release experiment. The reactants of the oxidation reactor can be selected from at least one of oxygen-containing organic matter, nitrogen-containing organic matter, alkanes, aromatics, alkenes, alkynes,H2O , CO,H2S , etc., but are not limited to these substances; the reactants in the reduction reactor can be selected from at least one of oxygen-containing organic matter, nitrogen-containing organic matter, nitrogen oxides, alkenes, alkynes, aromatics, protons,CO2 , CO, nitrogen, etc., but are not limited to these substances. In addition, when the oxidation reactor usesH2O and the reduction reactor uses protons, the oxidation reactor produces oxygen and the reduction reactor produces hydrogen, which is a double off-site water decomposition process.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供了一种“离场”电催化串联反应系统和操作方法，将复杂的催化反应从传统的电化学反应池中转移到电池外部的反应器中，避免了反应物或产物对电极、隔膜、催化剂等的污染，保证了整个系统的稳定运行，具有实际应用价值。同时，由于避免了电极、隔膜、催化剂等的污染而造成的失活，因此“离场”电催化反应技术也可以用到基础理论研究，得到本征的催化活性和催化剂结构的关联。本发明电池反应操作系统的创新，不仅推动了基础研究方面的发展，而且具有实际的应用价值，可以确保电池反应系统的稳定操作和长时间运行。The present invention provides an "off-site" electrocatalytic series reaction system and operation method, which transfers complex catalytic reactions from traditional electrochemical reaction cells to reactors outside the battery, avoiding the contamination of electrodes, diaphragms, catalysts, etc. by reactants or products, ensuring the stable operation of the entire system, and having practical application value. At the same time, since the deactivation caused by contamination of electrodes, diaphragms, catalysts, etc. is avoided, the "off-site" electrocatalytic reaction technology can also be used in basic theoretical research to obtain the correlation between intrinsic catalytic activity and catalyst structure. The innovation of the battery reaction operating system of the present invention not only promotes the development of basic research, but also has practical application value, which can ensure the stable operation and long-term operation of the battery reaction system.
图1为本发明实施例提出的离场电催化反应方法示意图。FIG1 is a schematic diagram of an off-site electrocatalytic reaction method according to an embodiment of the present invention.
下面结合具体的实施例，进一步阐述本申请。以下所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如下，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The following is a further description of the present application in conjunction with specific embodiments. The following are only a few embodiments of the present application and are not intended to limit the present application in any form. Although the present application is disclosed in the following preferred embodiments, they are not intended to limit the present application. A technician, without departing from the scope of the technical solution of this application, making slight changes or modifications using the technical contents disclosed above are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
如无特别说明，本申请的实施例中的原料均通过商业途径购买，不经任何特殊处理直接使用。Unless otherwise specified, the raw materials in the examples of the present application were purchased from commercial sources and used directly without any special treatment.
实施例1(离场电催化串联方法：苯制己二酸)Example 1 (Off-site electrocatalytic series method: benzene to adipic acid)
具体实验步骤如下：采用液流电解池，阳极和阴极电极均为固体石墨棒，阳极和阴极均使用水和乙酸乙酯混合溶剂(体积比8：2)的H2SO4溶液为电解液(cH2SO4＝3mol/L)，阳极的离子对是Ce(IV)/Ce(III)，Ce的摩尔浓度是0.5mol/L，阴极的离子对是四氢型硅钨酸/六氢型硅钨酸，硅钨酸的摩尔浓度是0.5mol/L，使用Nafion117(杜邦商业化隔膜)为隔膜。The specific experimental steps are as follows: a liquid flow electrolytic cell is used, the anode and cathode electrodes are solid graphite rods, the anode and cathode useaH2SO4 solution of a mixed solvent of water and ethyl acetate (volume ratio 8:2) as the electrolyte (cH2SO4 = 3mol/L), the ion pair of the anode is Ce(IV)/Ce(III), and the molar concentration of Ce is 0.5mol/L, the ion pair of the cathode is tetrahydrosilicotungstic acid/hexahydrosilicotungstic acid, and the molar concentration of silicotungstic acid is 0.5mol/L, and Nafion117 (DuPont commercial diaphragm) is used as the diaphragm.
S1：氧化反应器的反应物是苯，采用釜式反应器，温度为25℃，Ce(IV)溶液和苯(n苯:nCe＝3:7)同时通入反应器中，催化剂是RuOx/C。反应4h后，采用静置法，使水和乙酸乙酯溶剂分离，此时苯和苯酚溶解于乙酸乙酯中，通过气相色谱分析法，得到苯的转化率为99％，苯酚选择性为98％，通过实验室微型精馏器分离苯原料和苯酚产物。相应的Ce(III)进一步进入阳极槽进行氧化再生。S1: The reactant of the oxidation reactor is benzene. A tank reactor is used. The temperature is 25°C. Ce(IV) solution and benzene (nbenzene :nCe = 3:7) are introduced into the reactor at the same time. The catalyst is RuOx /C. After 4 hours of reaction, the water and ethyl acetate solvents are separated by a standing method. At this time, benzene and phenol are dissolved in ethyl acetate. By gas chromatography analysis, the conversion rate of benzene is 99% and the selectivity of phenol is 98%. The benzene raw material and the phenol product are separated by a laboratory micro-rectifier. The corresponding Ce(III) further enters the anode tank for oxidation regeneration.
S2：将苯酚产物和六氢硅钨酸通入到还原反应器中，采用釜式反应器，温度为25℃，六氢型硅钨酸溶液和苯酚摩尔比为n苯酚:n六氢型硅钨酸＝1:3，催化剂是Pd/C。反应1h后，采用静置法，使水和乙酸乙酯溶剂分离，此时苯酚和环己酮溶解于乙酸乙酯中，通过气相色谱分析法，得到苯酚的转化率为60％，环己酮选择性为92％，通过实验室微型精馏器分离苯酚和环己酮。相应的四氢型硅钨酸进一步进入阴极槽进行还原再生。S2: Phenol product and hexahydrosilicotungstic acid are introduced into a reduction reactor, using a tank reactor, the temperature is 25°C, the molar ratio of hexahydrosilicotungstic acid solution to phenol isnphenol :nhexahydrosilicotungsticacid =1:3, and the catalyst is Pd/C. After 1h of reaction, the water and ethyl acetate solvents are separated by a standing method. At this time, phenol and cyclohexanone are dissolved in ethyl acetate. By gas chromatography analysis, the conversion rate of phenol is 60%, and the selectivity of cyclohexanone is 92%. Phenol and cyclohexanone are separated by a laboratory micro-rectifier. The corresponding tetrahydrosilicotungstic acid further enters the cathode tank for reduction regeneration.
S3：随后将环己酮通入氧化反应器(返回S1中系统)中，采用釜式反应器，温度为40℃，Ce(IV)溶液和环己酮(n环己酮:nCe＝1:7)同时通入反应器中，搅拌2h后，采用静置法，使水和乙酸乙酯溶剂分离，此时环己酮和己二酸溶解于乙酸乙酯中，通过液相色谱分析法，得到环己酮的转化率>99％，己二酸选择性为100％，因为己二酸微溶于水，溶于乙酸乙酯，通过蒸馏脱除乙酸乙酯即可得到己二酸，产品纯度99％。相应的生成的Ce(III)进一步进入阳极槽进行氧化再生。S3: Cyclohexanone is then introduced into an oxidation reactor (returning to the system in S1), using a tank reactor at a temperature of 40°C, Ce(IV) solution and cyclohexanone (ncyclohexanone :nCe =1:7) are introduced into the reactor at the same time, and after stirring for 2 hours, water and ethyl acetate solvent are separated by a standing method. At this time, cyclohexanone and adipic acid are dissolved in ethyl acetate, and analyzed by liquid chromatography. The conversion rate of cyclohexanone is >99%, and the selectivity of adipic acid is 100%. Because adipic acid is slightly soluble in water and soluble in ethyl acetate, adipic acid can be obtained by removing ethyl acetate by distillation, and the product purity is 99%. The corresponding generated Ce(III) further enters the anode tank for oxidation regeneration.
实施例2(离场电催化串联方法中的苯氧化制苯酚)Example 2 (Benzene Oxidation to Phenol in an Off-site Electrocatalytic Series Method)
实施例2步骤与实施例1相同，该实施例为苯制苯酚的活性优化过程，具体过程如下；氧化反应器的反应物是苯，采用釜式反应器，温度为25℃，不同的氧化还原媒介体溶液和苯(n苯:n媒介体＝2:8)同时通入氧化反应器中，添加10％的三氟乙酸有机酸，促进苯酚生成，催化剂是RuOx/C。反应1h后，采用静置法，使水和乙酸乙酯溶剂分离，此时苯和苯酚溶解于乙酸乙酯中，通过气相色谱分析法，得到苯的转化率和苯酚选择性，通过实验室微型精馏器分离苯原料和苯酚产物。相应的氧化还原媒介体进一步进入阳极槽进行氧化再生。不同氧化还原媒介体下的苯转化和苯酚选择性如下表1所示。The steps of Example 2 are the same as those of Example 1. This example is an activity optimization process for preparing phenol from benzene. The specific process is as follows: the reactant of the oxidation reactor is benzene. A kettle reactor is used. The temperature is 25°C. Different redox mediator solutions and benzene (nbenzene :nmediator = 2:8) are simultaneously introduced into the oxidation reactor. 10% trifluoroacetic acid organic acid is added to promote the formation of phenol. The catalyst is RuOx /C. After 1 hour of reaction, the water and ethyl acetate solvents are separated by a standing method. At this time, benzene and phenol are dissolved in ethyl acetate. The conversion rate of benzene and the selectivity of phenol are obtained by gas chromatography analysis. The benzene raw material and the phenol product are separated by a laboratory micro-rectifier. The corresponding redox mediator further enters the anode tank for oxidation regeneration. The benzene conversion and phenol selectivity under different redox mediators are shown in Table 1 below.
表1.不同氧化还原媒介体下的苯转化率和苯酚选择性
Table 1. Benzene conversion and phenol selectivity under different redox mediators
注：电子媒介体利用率为传递电子到产物中的百分数。Note: Electron mediator utilization is the percentage of electrons transferred to the product.
实施例3(离场电催化串联方法中的苯酚还原制环己酮)Example 3 (Phenol reduction to cyclohexanone in an off-site electrocatalytic series method)
实施例3步骤与实施例1相同，该实施例为苯酚还原制环己酮的活性优化过程；具体过程如下，将苯酚产物和氧化还原媒介体通入到还原反应器中，采用釜式反应器，温度为25℃，苯酚和氧化还原媒介体溶液摩尔比为n苯酚:n媒介体＝1:3或1：5，催化剂是Pd/C，在催化剂表面接枝正辛醇来调变催化剂表面亲疏水性，进而调变催化活性。反应1h后，采用静置法，使水和乙酸乙酯溶剂分离，此时苯酚和环己酮溶解于乙酸乙酯中，通过气相色谱分析法，得到苯酚的转化率和环己酮选择性，通过实验室微型精馏器分离苯酚和环己酮。相应的氧化态氧化还原媒介体进一步进入阴极槽进行还原再生。不同氧化还原媒介体下的苯酚转化和环己酮选择性如下表2所示。The steps of Example 3 are the same as those of Example 1. This example is an activity optimization process for reducing phenol to cyclohexanone. The specific process is as follows: the phenol product and the redox mediator are introduced into a reduction reactor, a kettle reactor is used, the temperature is 25° C., the molar ratio of phenol to the redox mediator solution isnphenol :nmediator =1:3 or 1:5, the catalyst is Pd/C, and the catalyst is The surface is grafted with n-octanol to adjust the hydrophilicity and hydrophobicity of the catalyst surface, thereby adjusting the catalytic activity. After 1 hour of reaction, the water and ethyl acetate solvents are separated by the static method. At this time, phenol and cyclohexanone are dissolved in ethyl acetate. The conversion rate of phenol and the selectivity of cyclohexanone are obtained by gas chromatography analysis, and phenol and cyclohexanone are separated by a laboratory micro-distillation device. The corresponding oxidized redox mediator further enters the cathode tank for reduction regeneration. The phenol conversion and cyclohexanone selectivity under different redox mediators are shown in Table 2 below.
表2.不同氧化还原媒介体下的苯酚转化率和环己酮选择性
Table 2. Phenol conversion and cyclohexanone selectivity under different redox mediators
注：电子媒介体利用率为传递电子到产物中的百分数。Note: Electron mediator utilization is the percentage of electrons transferred to the product.
实施例4(离场电催化串联方法中的环己酮氧化制己二酸)Example 4 (Oxidation of cyclohexanone to adipic acid in an off-site electrocatalytic series method)
实施例4步骤与实施例1相同，该实施例为环己酮氧化制己二酸的活性优化过程；具体过程如下，将环己酮和氧化还原媒介体通入到氧化反应器中，采用釜式反应器，温度为40℃，环己酮和氧化还原媒介体溶液摩尔比为n环己酮:n媒介体＝1：7，搅拌2h后，采用静置法，使水和有机溶剂分离，此时环己酮和己二酸溶解于有机溶剂中，通过液相色谱分析法，得到环己酮的转化率和己二酸选择性。因为己二酸微溶于水，溶于乙酸乙酯等溶剂，采用乙酸乙酯为萃取剂，通过蒸馏脱除乙酸乙酯即可得到己二酸，产品纯度不低于99％。相应的生成的还原态氧化还原电子媒介体进一步进入阳极槽进行氧化再生。不同氧化还原媒介体下的环己酮转化和己二酸选择性如下表3所示。The steps of Example 4 are the same as those of Example 1. This example is an activity optimization process for oxidizing cyclohexanone to produce adipic acid. The specific process is as follows: cyclohexanone and a redox mediator are introduced into an oxidation reactor using a kettle reactor at a temperature of 40°C. The molar ratio of cyclohexanone and the redox mediator solution isncyclohexanone :nmediator =1:7. After stirring for 2 hours, the water and organic solvent are separated by standing. At this time, cyclohexanone and adipic acid are dissolved in the organic solvent. The conversion rate of cyclohexanone and adipic acid selectivity are obtained by liquid chromatography analysis. Because adipic acid is slightly soluble in water and soluble in solvents such as ethyl acetate, ethyl acetate is used as an extractant. Adipic acid can be obtained by removing ethyl acetate by distillation. The product purity is not less than 99%. The corresponding generated The reduced redox electron mediator further enters the anode tank for oxidation regeneration. The cyclohexanone conversion and adipic acid selectivity under different redox mediators are shown in Table 3 below.
表3.不同氧化还原媒介体下的环己酮转化率和己二酸选择性
Table 3. Cyclohexanone conversion and adipic acid selectivity under different redox mediators
注：电子媒介体利用率为传递电子到产物中的百分数。Note: Electron mediator utilization is the percentage of electrons transferred to the product.
如图1所示，本发明实施例1～4的反应系统可成功实现苯制己二酸，且中间产物、最终产物的收率和转化效果均已达到实际使用要求。本发明实施例1～4的电催化系统包含电池系统、氧化反应器、还原反应器、萃取器和精馏塔等。氧化反应器和还原反应器的产物和氧化还原媒介体通过有机溶剂萃取分离，回到阳极槽和阴极槽的氧化还原媒介体不含有反应物和产物，避免了对电极、隔膜等的污染。这种将反应物和产物与电极和隔膜分离，且将氧化反应器和还原反应器串联在一起的操作方法，就是本发明提出的新的电催化反应技术，称之为“离场”电催化串联反应技术。这个“离场”电催化反应系统不仅在基础研究的实验室方面可以进行基础理论研究，而且电池放大不需要因为放大效应而引起的对流道、内部结构工艺的调整，氧化和还原反应器在工业上非常成熟，易于放大，因此也可以进行电化学示范、中试、应用等尺度下的工业测试。As shown in FIG1 , the reaction systems of Examples 1 to 4 of the present invention can successfully realize the production of adipic acid from benzene, and the yield and conversion effect of the intermediate product and the final product have reached the actual use requirements. The electrocatalytic systems of Examples 1 to 4 of the present invention include a battery system, an oxidation reactor, a reduction reactor, an extractor, a distillation tower, etc. The products and the redox media of the oxidation reactor and the reduction reactor are separated by organic solvent extraction, and the redox media returned to the anode tank and the cathode tank do not contain reactants and products, thereby avoiding contamination of electrodes, diaphragms, etc. This operation method of separating reactants and products from electrodes and diaphragms and connecting the oxidation reactor and the reduction reactor in series is the new electrocatalytic reaction technology proposed by the present invention, which is called the "off-site" electrocatalytic series reaction technology. This "off-site" electrocatalytic reaction system can not only conduct basic theoretical research in the laboratory of basic research, but also the battery amplification does not require the adjustment of the convection channel and the internal structure process caused by the amplification effect. The oxidation and reduction reactors are very mature in industry and easy to amplify, so industrial tests at scales such as electrochemical demonstration, pilot test, and application can also be carried out.
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above are only several embodiments of the present application, and are not intended to limit the present application in any form. Although the present application is disclosed with preferred embodiments as above, it is not intended to limit the present application. Please note that any technician familiar with this profession, without departing from the scope of the technical solution of this application, using the above-disclosed technical content to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
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