An electrocatalytic reactor for synthesizing fuels from biomass and its derived molecules

Abstract

The present invention relates to an electrocatalytic reactor for synthesizing fuel from biomass and its derived molecules, which includes an electrolysis unit, an electrolyte circulation unit and a cooling unit. The electrolysis unit includes an anode chamber shell, an anode chamber membrane reinforcement sheet, a proton exchange membrane, a cathode chamber membrane reinforcement sheet and a cathode chamber shell arranged in sequence. The anode chamber shell and the cathode chamber shell are both divided into two connected chambers by a cooling water tank channel recessed inwardly on the shell surface. The anode and cathode chamber shells are used to contain anode and cathode electrolyte liquids and corresponding anode and cathode electrode sheets, respectively. The present invention improves the structure of each component of the device and their arrangement methods. Compared with the prior art, the present invention solves the problems of many by-products, unbalanced internal pressure, difficult replacement of electrodes and complex cooling in the electrosynthesis process. The manufacturing is simple and suitable for mass production of reactors and their products.

Description

Technical Field

[0001] The present invention belongs to the field of biomass energy utilization, and more specifically, relates to a design of a reactor for synthesizing low-carbon fuels from biomass and its derived molecules using electricity. Background Art

[0002] With the reduction of fossil fuel supply and the increasing environmental problems, biomass is considered to be a promising fuel source. Biomass has high energy reserves, is clean and renewable, and is a highly promising alternative energy source. At present, the use of biomass rapid pyrolysis to produce bio-oil, fuel gas, biochar, etc. has become an effective way to utilize biomass resources. However, due to the characteristics of high viscosity, high moisture, high oxygen content, corrosiveness and chemical instability of bio-oil, its direct application is limited. Therefore, bio-oil should be hydrated and upgraded before being used to produce liquid fuels. Traditional hydrogenation and upgrading processes are carried out at high temperatures. However, bio-oil is prone to polymerization when heated. Due to its thermal instability at high temperatures, bio-oil polymerizes to form coke, which blocks the active sites of the catalyst and the reactor, affecting the stability of the upgrading process.

[0003] For electrosynthetic fuels, simple electrosynthesis reactors have been demonstrated before. Most demonstrations have been performed at laboratory scale. Reactors have been demonstrated "membraneless", or they can use membranes that exchange protons (proton exchange membranes, PEM) or hydroxyl ions (alkaline exchange membranes, AEM). Most commonly, these electrosynthesis reactors are used to produce hydrogen via a water splitting reaction, with oxygen as a byproduct. Large-scale industrial-scale water splitting electroanalyzers have been demonstrated and are commercially available. Recently, the production of CO from CO has been demonstrated. 2 and H 2 Electrosynthesis of syngas (CO and H 2 ), the by-product is H 2 O. These demonstrations are usually limited to laboratory scale. There are currently no industrial-scale membrane reactors capable of hydrogenating and upgrading biologically derived molecules obtained from biomass directly using electricity. In terms of fuels, this means the production of alkanes, alkenes, alcohols or similar from the original molecules of biomass. Here, biomass is defined as any plant or animal matter that has recently obtained its carbon from atmospheric CO2 (e.g. wood, agricultural waste and by-products, food waste and by-products, municipal solid waste, straw, potatoes, corn cobs, rice husks, etc.), rather than fossil carbon from petroleum products. However, the concept of laboratory-scale demonstrations of electrocatalytically driven biomass conversions to increase the value of biomolecules has been proven in previous studies.

[0004] The typical structure of a membrane reactor in electrocatalytic synthesis is similar to that of a proton exchange membrane fuel cell and / or an electrolyzer. A membrane reactor generally includes: 1) a proton exchange membrane (such as sodium ions), 2) a catalyst material, and 3) an electrolyte solution.

[0005] Electrode catalysts are also an important part of it, and several materials have been confirmed and used as catalyst materials. Pure metals include Pt, Ru, Ni, Co, Fe, Cr, Pd, and Ir. These pure metals are usually deposited in the form of thin films on low-cost conductive substrates (such as stainless steel or carbon). Metal particles of various sizes from micrometers to nanometers are also used as catalysts. These small particles are usually coated on a conductive material or "substrate". The conductive materials used include stainless steel, carbon (such as graphite, hard / glassy carbon), nickel foam, etc. Metal oxides and metal hydroxides are also used as catalysts, the most famous of which are iron hydroxide and nickel-doped compounds. These are mainly used for water splitting to produce hydrogen, and have limited applications in carbon dioxide emission reduction and biomass conversion upgrading.

[0006] Electrolytes used for electrocatalysis can be alkaline, acidic, or salt-based. The vast majority of electrolytes are alkaline solutions with a high pH (>7). These are primarily used for water splitting. Acid catalysis has also been demonstrated on a laboratory scale. However, even on a laboratory scale, acid catalysis is considered an underdeveloped technology. Electrocatalytic synthesis of fuels and value-added chemicals in an acidic environment on an industrial scale has not yet been demonstrated. On an industrial scale, alkalinity is typically provided by NaOH or KOH solutions. Alkaline electrolyzers for water splitting are the most mature technology, and these have been applied on an industrial scale to produce green hydrogen at a significant price premium over fossil hydrogen.

[0007] Conventional hydrogenation of bio-derived molecules: Molecules from biomass can be converted into useful fuels by thermal processes at high temperatures and pressures over appropriate catalysts. This is a hydrogenation process where typically gaseous hydrogen molecules react with biomolecules. The gaseous molecular hydrogen is produced separately. The need for gaseous hydrogen limits the opportunities for decarbonization of this standard hydrogenation process as the cost of this green electrocatalytic hydrogen is still too high to achieve low commercialization and is expected to remain uncompetitive for at least the next 7-15 years. There may be some minimal commercial penetration of this technology where cheap fossil hydrogen (usually from natural gas reforming) can be used to hydrogenate existing hydrocarbons from biomass. This has been successfully used in the so-called "hydrogenated fatty acids and fatty acids" (HEFA) pathway to produce biodiesel fuel blends with up to 20% biomass feedstock utilization. The process converts fatty acids and biodiesel esters into pure long-chain liquid alkanes by hydrogenation. However, large biomass fractions cannot usually be used in these processes because their catalysts, which convert fossil fuels and large free fatty acid fractions, have a tendency to cause plugging and fouling in typical processes. The capital costs of these conventional fossil fuel hydrogenation systems are high (approximately $500 million), and the owners and operators of these systems are typically large fossil fuel companies that are unwilling to process large quantities of bio-derived molecules through existing systems. Neste, one of the leading companies in biomass hydrogenation, owns a large (approximately 1 billion liters / year) biomass hydrogenation plant in Singapore that uses fossil hydrogen produced by natural gas reforming. The selling price of this biofuel is still approximately 4 times higher than conventional diesel, mainly due to relatively high feedstock prices, which indicates that this technology cannot make liquid biofuels competitive with existing fossil fuels. In summary, there are many obstacles to producing large quantities of liquid biofuels using conventional hydrogenation technologies, and these systems are unable to handle large-scale biofuel synthesis conversion reactions.

[0008] The use of electricity to transform bioderived molecules in simple reactors has been demonstrated. The molecules transformed include vegetable oils, long chain fatty acids, medium chain fatty acids, and a variety of other less common molecules. Valorization of molecules typically converts the molecules into products suitable for use in industries other than energy (pharmaceuticals / health care, polymers / plastics, chemicals, etc.). Under these conditions, the molecules are typically deoxygenated and converted to alkanes, alkenes, alcohols, or similar substances. While reports of direct conversion of biomolecules to alkane or alkene fuels are relatively limited, they have been demonstrated. Currently, there are no industrial-scale systems suitable for the electrosynthesis and conversion of bioderived molecules into high-quality fuels.

[0009] It is well known that laboratory-scale membrane-based reactor cases also have many problems. Among these problems, pressure imbalance leads to membrane strain, thinning, plastic deformation and tearing, which is caused by the generation of bubbles on one side of the sealed flow cell reactor relative to the other side. Membrane fouling caused by contact with organic matter is also considered a major problem that limits its application in large-scale industrial systems. Reactor cooling methods related to industrial-scale systems are also not well developed. Simple methods for replacing and recycling deactivated catalysts at electrodes are also not well developed and have not been demonstrated in detail.

[0010] In view of the above situation, we have designed a reactor for the synthesis of low-carbon fuels from biomass and its derived molecules under mild conditions based on electrochemistry. In this process, bio-oil produced by pyrolysis is not utilized because it requires external energy input and does not produce uniform and homogeneous organic products as mentioned above. Instead, acid hydrolysis is used to hydrolyze cellulose and starch to obtain high and uniform individual molecules, mainly simple carbohydrates / sugars, which can be directly dissolved in water-based electrolyte solutions. Subsequently, these sugars are electrocatalytically converted into alkane fuels through various deoxygenation steps. The process involves the removal of oxygen from these cellulose-derived molecules using various electrocatalytic steps. These steps include the removal of double-bonded oxygen and hydroxyl (-OH) groups from the electrolytic medium using corrosion-resistant metal (platinum (111), nickel, titanium, alloy) catalysts. Subsequently, molecules with longer carbon chain lengths are synthesized from the remaining fatty acids in an alkaline electrolyte medium (Kolbe reaction) using a flat platinum (111) electrode. The hydrocarbon molecules produced by this process are oxygen-free and suitable for use as alternative fuels for diesel and gasoline engines. Summary of the invention

[0011] In view of the above defects or improvement needs of the prior art, the purpose of the present invention is to provide an electrocatalytic reactor for synthesizing fuels from biomass and its derived molecules. The reactor design of the present invention solves the problems of many by-products, unbalanced internal pressure, difficult replacement of electrodes and complex cooling during the electrosynthesis process. It is simple to manufacture and suitable for mass production of reactors and their products. The electrocatalytic reactor device includes an electrolysis unit, an electrolyte circulation unit and a cooling unit, and the components arranged in each unit are interconnected.

[0012] The electrolysis unit comprises an anode chamber shell, an anode chamber membrane reinforcement sheet, a proton exchange membrane, a cathode chamber membrane reinforcement sheet and a cathode chamber shell, wherein an anode chamber membrane reinforcement sheet and a cathode chamber membrane reinforcement sheet are arranged between the anode chamber shell and the cathode chamber shell, and a proton exchange membrane is arranged between adjacent anode chamber membrane reinforcement sheets and cathode chamber membrane reinforcement sheets; the anode chamber shell and the cathode chamber shell are both divided into two connected chambers by a cooling water tank channel recessed inwardly from the outer surface of the shell; the anode chamber shell is used to contain anode electrolyte liquid, and an anode electrode sheet is installed therein; the cathode chamber shell is used to contain cathode electrolyte liquid, and a cathode electrode sheet is installed therein; the electrolysis unit provides direct current to the anode chamber and the cathode chamber respectively through the anode electrode sheet and the cathode electrode sheet, the anode chamber undergoes an oxidation reaction to produce oxygen and protons, the protons reach the cathode chamber through the proton exchange membrane, and the biomolecules dissolved in the cathode chamber undergo an electrochemical hydrogenation reaction to obtain fuel and value-added chemicals.

[0013] The salt in the electrolyte liquid in the anode chamber can be selected from common salts in the art, so that the electrolyte is conductive, and the pH is adjusted by acid or base, and oxygen is released in the anode chamber. The cathode chamber also contains salts and acids or bases, but its main function is to accommodate dissolved biomolecules and react them, which will be reduced by the electrocatalytic analysis process. Salts in the electrolyte solution include but are not limited to Na, K and Mg, sulfates, chlorides, acetates and phosphates. The electrolytes on the anode oxidation side and the cathode reduction side are both alkaline or acidic, and the alkalinity will be provided by NaOH or KOH solutions. Acidity will be provided by acids, including but not limited to sulfuric acid, acetic acid, and phosphoric acid. The electrolyte also includes additives for improving the suspension and / or separation of liquid products, which include methanol, ethanol, acetate, acetate, isopropanol, acetone, choline, glycerol and / or biologically derived byproducts in the reactor electrosynthesis process.

[0014] The electrolyte circulation unit includes an electrolyte inlet, an electrolyte outlet and an electrolyte pumping assembly arranged on both the anode chamber housing and the cathode chamber housing. The electrolyte pumping assembly connects the electrolyte inlets and electrolyte outlets corresponding to each other in the cathode and cathode housings, so that the electrolyte circulates through the reactor. Since a plurality of corresponding electrolyte inlets and electrolyte outlets are arranged on the side of each housing, in order to facilitate the advantages of the housing chamber structure, when in use, it is stipulated that the electrolyte inlet and the electrolyte outlet are respectively from different chambers separated by cooling water channels in the corresponding housing. The electrolyte pumping assembly is located outside the electrolysis unit, including a cathode electrolyte pumping assembly and an anode electrolyte fluid pumping assembly. The device includes at least one electrolyte peristaltic pump (e.g., a high performance liquid chromatography "HPLC" pump) and a container for storing different electrolytes. The pumping assembly connects the electrolyte inlet of the cathode chamber housing to the electrolyte outlet so that the electrolyte fluid moves through the reactor, which will enter the electrocatalytic reactor chamber through the inlet of the unreacted biomolecules and enter the subsequent separation and purification process through the outlet. The electrolyte inlet of the anode chamber is connected to the electrolyte outlet through the anode electrolyte fluid pumping assembly to form a circulation loop. Purified water (e.g., deionized water, distilled water) is added to this circulation loop to replenish the water used in the electrocatalytic process, which converts water into oxygen and protons.

[0015] The cooling device includes a cooling water tank channel that is recessed inwardly on the shell surface of the anode chamber shell and the cathode chamber shell, a cooling water inlet and a cooling water outlet located at both ends of the cooling water tank channel, and a corresponding anode cooling water tank cover and cathode cooling water tank cover located at the upper part of the cooling water tank channel. The cooling unit is used to cool the electrode sheets in the anode and cathode chambers. Since the reactor is a symmetrical structure, the anode is used as an example for explanation here. The cathode structure and function are the same as it, so it will not be repeated. The cooling unit is used to cool the anode electrode sheet in the anode chamber. Water enters the cooling water inlet, flows through the cooling water tank channel and flows out from the cooling water outlet. An independent water circulation unit connects the cooling water inlet and outlet in a closed loop, passing through a chiller that reduces the heat in the water fluid. The thickness of the material at the bottom of the cooling water tank channel that contacts the electrode plate is minimized to ensure good thermal contact with the electrode material opposite the channel. This is to reduce the temperature of the electrode, and the benefit is that the lower temperature reduces the number of byproducts of the electrocatalytic process. At high flow rates, a large amount of current is discharged through the electrolyte. Since the electrolyte is the most resistive part of the path of the current through the reactor, it naturally heats up when large amounts of power are passed through it at high flow rates suitable for industrial processes. This property increases the yield of desired fuels by allowing dissolved biomolecules to be electrochemically hydrogenated under pre-set temperature conditions.

[0016] A conductive path connects the anode electrode through a bolt that passes through the power supply and connects to the cathode electrode through a similar bolt. The electrodes are then powered by a conductive electrolyte solution that passes through the proton exchange membrane to the cathode electrode.

[0017] Furthermore, the cooling water tank channel is square, and the cathode chamber and anode chamber surrounded by the cooling water tank channel and the cathode / anode chamber shell are inner tanks with square grooves, and the inner tanks are respectively anode and cathode liquid flow chambers, and the cathode and cathode electrolyte inlets are located in the lower half of the side of the inner tank, and the electrolyte outlet is located in the upper half of the side of the inner tank. The electrolyte inlet and electrolyte outlet of the anode chamber and cathode chamber are located on both sides of the chamber, and the electrolyte inlet and outlet of the anode chamber and cathode chamber do not interfere when connected to the outer tube. In addition, the electrolyte outlet, electrolyte inlet, cooling water outlet, cooling water inlet and other inlets and outlets on both sides of the cathode chamber and the anode chamber are all designed with threaded ports. This design allows the closure and opening states of the inlets and outlets to be flexibly adjusted according to specific usage requirements. According to the need for discharge (gas or liquid), when discharge (gas or liquid) is required, the inlet and outlet can be opened by loosening the sealing bolts; and when discharge (gas or liquid) is not required, the inlet and outlet can be tightly closed by tightening the sealing bolts.

[0018] Furthermore, a labyrinth turbulent structure is provided at the bottom of the anode chamber and the cathode chamber, so that the anode and cathode liquids generate local reflux in the reaction chamber, thereby improving the uniformity of the liquid in the chamber and prolonging the reaction time of the liquid on the electrode surface.

[0019] Furthermore, the protruding position of the middle part of the inner groove of the anode and cathode chamber is provided with parallel strips that are concave outward and have a certain spacing. The direction of the strips is perpendicular to the axial direction of the cooling water tank channel. The parallel strips are installed with adapted anode and cathode electrode sheets. The size range of the electrode sheets is 5-50mm in width, 0.1-3mm in thickness and 50-1250mm in length. The spacing between the electrodes is 3-5cm to improve the efficiency of electrocatalysis. A cathode and cathode electrolyte gap layer is retained between the anode and cathode electrode sheets and the anode and cathode chamber membrane reinforcement sheets to allow the electrolyte to pass. For the cathode, the biomolecules suspended in the water-based electrolyte solution fill the inflow cavity and continue to enter the electrolyte gap layer. An electric current is applied to remove oxygen from the biomolecules in contact with the electrode, and the catalyst on the electrode adds hydrogen to the molecule, removing oxygen and producing water as a product.

[0020] Further, holes are perforated in the anode and cathode chamber membrane reinforcement sheets at positions directly opposite to the cathode and cathode electrolyte gap layers to allow contact with the electrolyte solution. After the biomolecules are converted in the electrocatalytic channel, the electrolyte solution with the converted molecules flows into the overflow chamber and out of the reactor. The converted molecules are more hydrophobic or insoluble in water than the original biomolecules and can be easily separated from the water-based electrolyte. The easy separation of the fuel products is another advantage of this design. Gravity-assisted separation and membrane protection can be directly combined here, and tilting the direction of the reactor shell unit can prevent hydrophobic molecules from contacting the electrodes or membranes.

[0021] Further, a two-way pressure valve is provided above each of the anode and cathode chamber shells, and a drain port is provided below each. A two-way pressure valve is provided at the top of the chamber to regulate the pressure during the electrocatalytic process, and it can be either inflated or deflated according to the pressure balance requirements. Due to the evolution of gases during the hydrogenation of biomolecules, the pressure changes. The gases (H2, CO2) produced during the reaction can be easily regulated in pressure by the two-way pressure valve. The flow rate and pressure of the overflow chamber are adjustable to ensure that there is always gas in the overflow chamber and no liquid is in contact with the two-way pressure valve. Through the two-way pressure valve, these gases can be collected and stored, or transported to further processes to produce more fuel (for example, electrocatalytic carbon dioxide reduction and Fischer-Tropsch synthesis fuel). The evolved oxygen can also be collected by an overpressure / pressure relief valve opposite the proton exchange membrane, which has the same configuration and valve on the membrane and reduction side. Most reactors do not describe the collection of gases, so this is also an important improvement over traditional reactors.

[0022] Furthermore, the cooling unit is a unit in which water flows through the reactor channel in close contact with the back side of the electrode material. The anode and cathode chamber shells are equipped with thermocouples and electronic thermostats. The temperature of the reactor is monitored according to the settings on the cooler. The thermocouples are used to detect the temperature of the electrolyte solution in the anode and cathode chamber shells. The thermostat is used to control the output power of the chiller according to the temperature detected by the thermocouples, and the power of the heating resistor wire in the anode and cathode chambers is changed to control the temperature of the electrolyte in the anode and cathode chambers.

[0023] Furthermore, in terms of materials or materials, the reactor system consists of two major parts, separated by a membrane reinforced by a perforated rigid plate. The membrane will achieve the exchange of protons, generally a commercial Nafion exchange membrane (brand: DuPont). The reactor half-plate and body will be made of stainless steel, aluminum or rigid and / or thermosetting polymers, including glass, nylon, polytetrafluoroethylene or similar materials. The fuselage itself is designed to withstand pressures of up to 120 pounds. The reactor contains narrow channels a few millimeters wide, through which reactants suspended in an electrolyte will flow.

[0024] The electrode substrate will be made of stainless steel or graphite and coated with a catalyst material. The catalyst material will be composed of metals, including but not limited to Pt(111), Co, Ni, Cu, Al, Zn, Pd, Ir, Sn, In, Mn, Fe, Sr, La, Ga, Mo, W, Ag, B, Ti, V, Bi, Pb. Alloys and combinations of these metals, such as combinations of copper, aluminum and nickel. Compounds of these metals include but are not limited to their oxides, hydroxides, hydroxides, sulfides, sulfur oxides, nitrides, nitrogen oxides, phosphides, phosphorus oxides, phosphates, borates, boron hydrates, fluorides or the like. High surface area electrodes can be used, including metal foams. Nanomaterials and complex nanocomposites of the above materials can be utilized. The electrodes can also be mounted directly on perforated separation / reinforcement sheets on the membrane. This facilitates the separation of products or organics in the lighter layers with less density at the top of the channel.

[0025] The applied current density was 50 mA / cm 2 and 500 mA / cm 2 between.

[0026] The flow is targeted to provide laminar flow with a velocity between 1 cm / sec and 10 cm / sec through the channel.

[0027] The two-way pressure valve will keep the pressure on both sides of the membrane at a constant value between 0.4 MPa and 3 MPa. It is this pressure regulation that avoids pressure imbalance causing membrane strain, thinning, plastic deformation and tearing.

[0028] The reactor operates between the freezing and boiling points of the electrolyte (-4-100°C).

[0029] Furthermore, the reactor of the present invention is applied to the synthesis of fuels and value-added chemicals from biomass and bioderived molecules, where biomass is any plant or animal matter that has recently obtained carbon from atmospheric carbon dioxide (e.g., wood, agricultural waste and byproducts, food waste and byproducts, municipal solid waste, straw, potato, corn cob, rice husk, etc.). The biomass is subjected to acid hydrolysis to obtain uniform single biomolecule raw materials, and the biomolecules obtained by hydrolysis include simple anhydrous compounds / sugars (e.g., glucose, fructose, xylose), furans, 5-hydroxymethylfurfural, cellobiose, mono- and polyols (e.g., sorbitol), mono- and di-acids (e.g., gluconic acid and gluconic acid), etc. These biomolecules can be directly dissolved in water-based electrolyte solutions. Subsequently, these biomolecule raw materials are electrocatalytically converted into alkane fuels through various deoxygenation steps, and the products obtained include saturated fatty acids (e.g., hexanoic acid), alkanes (e.g., hexane), alkenes (e.g., hexene), and alcohols (e.g., hexanol).

[0030] Compared with the prior art, the above technical solution conceived by the present invention can achieve the following beneficial effects:

[0031] Gravity-Assisted Organic Separation: The reactor will be adjusted so that gravity helps separate reacting species from unreacted species, forming a layer of less dense organic material in the channels that naturally rises away from the electrodes, reducing the likelihood of further electrocatalytic reactions with the electrode materials, thereby limiting the production of by-products and increasing selectivity.

[0032] Pressure balance: A simple two-way pressure valve is used to balance the pressure on both sides. The pressure on the oxygen evolution electrode side will be generated by generating oxygen bubbles and supplemented by a compressor as needed. The pressure on the biomolecule hydrogenation side will be generated by a compressor and supplemented by H 2 and simple volatile hydrocarbons (CH 4 , CO, formate, etc.) and any gaseous products.

[0033] Easy electrode replacement logic: The electrodes can be easily removed and replaced in the design because they can be detached and embedded in the body and can be separated into different reactors with low manufacturing costs.

[0034] Simplified electrode cooling: Electrosynthesis reactors can consume a lot of electricity in use. Therefore, the design actively cools the electrodes by simply flowing cooling water through the back of the electrode channels. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 An exploded view of a single reactor.

[0036] Figure 2 External view of a single reactor.

[0037] Figure 3 A three-dimensional view of the membrane and the perforated reinforcement sheet.

[0038] Figure 4 For water cooling channels and various inlet / outlet ports.

[0039] Figure 5 A side view of half of the reactor.

[0040] Figure 6 An angle view of the reactor's internal structure

[0041] Figure 7 A bottom view of the reactor shell.

[0042] Figure 8 Schematic diagram of the reactor: a) bottom, b) side, c) top view.

[0043] Fig. 9 Schematic diagram of the reactor channel: a) side view, b) end view

[0044] Fig.10 The raw material molecules are cellulose and hemicellulose and their derivatives.

[0045] Fig.11 Schematic diagram of the electrolyte flow in the cation and anode chambers: a) cathode chamber for biomolecule reduction reaction; b) anode chamber for producing oxygen.

[0046] Fig.12 Schematic diagram of the electrical connections of the reactor chamber, anode and cathode.

[0047] Figure 1-Figure 12 The meanings of the reference numerals are as follows:

[0048] Anode cooling water tank cover 1, anode chamber shell 2, anode chamber membrane reinforcement sheet 3, proton exchange membrane 4, cathode chamber membrane reinforcement sheet 5, cathode chamber shell 6, cathode cooling water tank cover 7, reinforcement sheet perforation 8, electrolyte inlet 9, electrolyte outlet 10, cooling water inlet 11, cooling water outlet 12, cooling water tank channel 13, electrode bolt hole 14, vent hole 15, anode electrode sheet 16, drain port 17, anode electrolyte gap layer 18, outflow cavity 19, inflow cavity 20, cathode electrolyte gap layer 21, cathode electrode sheet 22, two-way pressure valve 23, biomass raw material acid hydrolysis tank 24, fractionation and purification tank 25, electrolyte pumping assembly 26, conductive bolt 27, power supply 28. DETAILED DESCRIPTION

[0049] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0050] like Figure 1-Figure 2 , the present embodiment provides an electrocatalytic reactor for synthesizing fuels from biomass and its derived molecules, including an electrolysis unit, an electrolyte circulation unit and a cooling unit, the components arranged in each unit are interconnected, wherein: the electrolysis unit includes an anode chamber shell 2, an anode chamber membrane reinforcement sheet 3, a proton exchange membrane 4, a cathode chamber membrane reinforcement sheet 5 and a cathode chamber shell 6, an anode chamber membrane reinforcement sheet 3 and a cathode chamber membrane reinforcement sheet 5 are arranged between the anode chamber shell 2 and the cathode chamber shell 6, and a proton exchange membrane 4 is arranged between adjacent anode chamber membrane reinforcement sheets 3 and cathode chamber membrane reinforcement sheets 5;

[0051] like Figure 4 The anode chamber shell 2 and the cathode chamber shell 6 are divided into two communicating chambers by a cooling water tank channel 13 which is recessed inwardly on the outer surface of the shell;

[0052] like Figure 6 , Fig. 9 The anode chamber shell 2 is used to contain the anode electrolyte liquid, and an anode electrode sheet 16 is installed therein; the cathode chamber shell 6 is used to contain the cathode electrolyte liquid, and a cathode electrode sheet 22 is installed therein; the electrolysis unit provides direct current to the anode chamber and the cathode chamber respectively through the anode electrode sheet 16 and the cathode electrode sheet 22, and the anode chamber undergoes an oxidation reaction to produce oxygen and protons, and the protons reach the cathode chamber through the proton exchange membrane, and the biomolecules dissolved in the cathode chamber undergo an electrochemical hydrogenation reaction;

[0053] like Figure 4 , Fig.11 The electrolyte circulation unit includes an electrolyte inlet 9, an electrolyte outlet 10 and an electrolyte pumping assembly 26 disposed on both the anode chamber housing 2 and the cathode chamber housing 6. The electrolyte pumping assembly 26 connects the electrolyte inlet 9 and the electrolyte outlet 10 in the cathode and cathode housings. The electrolyte inlet 9 and the electrolyte outlet 10 come from different chambers separated by cooling water channels in the corresponding housings, respectively, so that the electrolyte circulates through the reactor. The cooling device includes a cooling water tank channel 13 disposed inwardly on the surface of the anode chamber housing 2 and the cathode chamber housing 6, a cooling water inlet 11 and a cooling water outlet 12 disposed at both ends of the cooling water tank channel 13, and an anode cooling water tank cover 1 and a cathode cooling water tank cover 7 disposed on the upper part of the cooling water tank channel 13.

[0054] like Figure 5-Figure 6 The cooling water tank channel 13 is square, and the cathode chamber and anode chamber surrounded by the cooling water tank channel 13 and the cathode / anode chamber shell are inner tanks with square grooves. The inner tanks are respectively the cathode and cathode liquid flow chambers, and the cathode and cathode electrolyte inlets are located in the lower half of the side of the inner tank, and the electrolyte outlet is located in the upper half of the side of the inner tank. The electrolyte inlet and electrolyte outlet of the anode chamber and cathode chamber are located on both sides of the chamber, and the electrolyte inlet and outlet of the anode chamber and cathode chamber do not interfere when connecting the outer tube. In addition, the electrolyte outlet, electrolyte inlet, cooling water outlet, cooling water inlet and other inlets and outlets on both sides of the cathode chamber and the anode chamber are all designed with threaded ports. According to the needs of discharge (gas or liquid), when discharge (gas or liquid) is required, the inlet and outlet can be opened by loosening the sealing bolts; and when discharge (gas or liquid) is not required, the inlet and outlet can be ensured to be tightly closed by tightening the sealing bolts. In particular, the electrolyte inlet 9 and the vent hole 15 can share a threaded opening, and when the indoor pressure is high and emergency venting is required, the vent hole 15 can be used as a quick venting channel.

[0055] The bottom of the anode chamber and the cathode chamber are provided with a labyrinth turbulent structure, so that the anode and cathode liquids generate local reflux in the reaction chamber, thereby improving the uniformity of the liquid in the chamber and prolonging the reaction time of the liquid on the electrode surface.

[0056] like Figure 6-Figure 7The protruding position of the middle part of the inner tank of the anode and cathode chamber is provided with a parallel strip belt that is concave outward and has a certain spacing. The direction of the strip belt is perpendicular to the axial direction of the cooling water tank channel. The parallel strip belt is installed with an adapted anode and cathode electrode sheet. The size range of the electrode sheet is 5-50mm in width, 0.1-3mm in thickness and 50-1250mm in length. The spacing between the electrodes is 3-5cm. A cathode and cathode electrolyte gap layer is reserved between the cathode and cathode electrode sheets and the cathode and cathode chamber membrane reinforcement sheets to allow the electrolyte to pass through.

[0057] like Figure 3 , holes are punched in the anode and cathode chamber membrane reinforcement sheets at positions directly opposite to the anode and cathode electrolyte gap layers to form reinforcement sheet perforations 8 to allow contact with the electrolyte solution.

[0058] like Figure 5-Figure 6 , Figure 8 , Fig.11 A two-way pressure valve 23 is provided above the anode and cathode chamber shells, and a drain port 17 is provided below each. According to the pressure balance requirements, both inflation and deflation can be performed. The two-way pressure valve 23 will keep the pressure on both sides of the membrane at a constant value between 0.4 MPa and 3 MPa.

[0059] like Figure 6 The cooling unit is a water flow through the cooling water tank channel 13 in close contact on the back of the electrode material. The anode and cathode chamber shells are equipped with thermocouples and electronic thermostats. The temperature of the reactor is monitored according to the settings on the cooler. The thermocouple is used to detect the temperature of the electrolyte solution in the anode and cathode chamber shells. The thermostat is used to control the output power of the chiller according to the temperature detected by the thermocouple, and the power of the heating resistor in the cathode chamber is changed to control the temperature of the electrolyte in the cathode chamber.

[0060] like Fig.11 , the electrolyte pumping assembly 26 is composed of an HPLC peristaltic pump and an electrolyte storage tank located on the pipeline. After the acid hydrolysis product biomolecules in the biomass raw material acid hydrolysis tank 24 are mixed with the cathode electrolyte, the pumping assembly connects the electrolyte inlet 9 of the cathode chamber shell with the electrolyte outlet 10 to move the electrolyte fluid through the reactor, which will allow the unreacted biomolecules to enter the electrocatalytic reactor chamber through the inlet and enter the subsequent fractionation purification tank 25 through the outlet for separation and purification. The electrolyte inlet 9 of the anode chamber is connected to the electrolyte outlet 10 through the electrolyte pumping assembly 26 to form a circulation loop. Pure water (e.g., deionized water, distilled water) is added to this circulation loop to supplement the water used in the electrocatalytic process, which converts water into oxygen and protons.

[0061] like Fig.12, a schematic diagram of the electrical connection of the reactor chamber, the anode and the cathode, the power supply 28 energizes the cathode electrode sheet 22 and the anode electrode sheet 16 through the conductive bolts 27 to perform an electrocatalytic reaction.

[0062] Standardized, “off-the-shelf” electrical and fluid connections and pressure valves can be used in the construction. The wires and electrical connections to the electrodes will be made via the extended screw connections shown in Figure 4.

[0063] In this example, the electrode substrate will be made of stainless steel or graphite and coated with a catalyst material. One or more of precious metals such as platinum, gold, palladium, etc. can be used as cathode catalyst materials; one or more of graphite, nickel, iron hydroxide, and nickel-doped compounds can be used as anode catalyst materials. The proton exchange membrane model in this embodiment is Nafion-117. Electrolyte preparation: The preparation method of the electrolyte is very simple. Just add reactants, salts, organic matter, etc. to water and use acid (such as H 2 SO 4 , acetic acid or similar substances) or alkali (NaOH, KOH) to adjust the pH value. In this example, the electrolytic salt solution can be a single acid or alkali dilute solution, or an inorganic salt and its buffer solution, such as potassium dihydrogen phosphate and dipotassium hydrogen phosphate buffer solutions, sodium carbonate and sodium bicarbonate buffer solutions.

[0064] The reactor body will have several ports. Reactant fuel and electrolyte outlets 10 and reactant and electrolyte inlets 9 such as Figure 4 and Figure 8 shown. Figure 4 Several ports are shown to make the design more symmetrical and configurable.

[0065] Gravity Feed and Product Separation: The reactor can be mounted in an orientation that allows the electrolyte channels to be perpendicular to the ground, parallel to the vector generated by gravity, or inclined to gravity to separate electrolyte and product using density differences between electrolyte channels.

[0066] Electrical connections: The electrodes can be connected to the reactor housing using long bolts. A voltage (0.3-5 V) can then be applied across the electrodes to obtain a current density between 50-500 mA / cm2.

[0067] Liquid flow and gas collection during operation: The large chambers above and below the anolyte gap layer 18 are mainly used to separate gas and liquid. In the outflow chamber 19, gas and liquid are separated by discharging product molecules (i.e. fuel) suspended in the electrolyte solution through the electrolyte outlet 10. The gas is collected by an overpressure or two-way pressure valve 23, such as Figure 8 shown.

[0068] Fig.10The raw material molecules, cellulose and hemicellulose and their derivatives are displayed. After acid hydrolysis of biomass, uniform single biomolecule raw materials are obtained. The biomolecules obtained by hydrolysis include cellulose, hemicellulose, hexose, hexonic acid, pentose, and deoxyhexonic acid. These molecules are subsequently converted into saturated fatty acids (such as hexanoic acid), alkanes (such as hexane), alkenes (such as hexene), and alcohols (such as hexanol) through the electrocatalytic hydrogenation process of this reactor. Through further electrolytic condensation, the carbon chain length can be extended from C5 to C6 to C8 to C10, or even longer fuel molecules.

[0069] The reactor has two operating modes: one is gravity feeding without suction, and the other is active suction of fluid through the system. All liquid in the reactor can be discharged through the drain port 17.

[0070] If the reactor is operated in a gravity feed configuration, the reactants are introduced into the top chamber and subsequently run downward through the channels where the electrosynthesis takes place. The gas bubbles (e.g., H) generated in the reactor channels by the electrocatalytic process 2 , O 2 , CO 2 , small organic molecules) will filter back through the reactant and electrolyte streams and the gas will be collected at the top of the reactor. This gas can exit the reactor and be collected through the exhaust / overpressure valve at the top of the reactor housing. The bottom chamber can then be filled with electrolyte and electrosynthesis products. These products can be collected as they flow out of the bottom of the reactor under gravity. As the fluid passes through the connection outlet at the bottom of the reactor, the flow rate can be controlled simply using the pipe diameter and connection throttling.

[0071] If the reactor is fed with a pump suitable for delivering chemicals and electrolytes at various pH values, the reactants will be introduced into the lower chamber of the reactor. When this lower chamber is full, the reactants will flow upwards through the electrosynthesis channel at a rate determined by the pumping rate. The gases produced during the electrosynthesis process will be collected, just like in the case of gravity feeding, the only difference is that now they are swept to the top chamber of the reactor with the flow of fluid. The fluid in the top chamber of the reactor contains the products and electrolytes. This can leave the reactor through the connections on both sides of the top chamber. These gases are again collected through the overpressure / vent valve at the top of the reactor.

[0072] A gravity-fed configuration is attractive because it requires minimal external energy to move the fluid. A pumped configuration can provide better control over fluid flow rates and potentially more efficient gas collection.

[0073] In both configurations, the pressure will be regulated by the fluid flow rate and a gas compressor connected to the top chamber.

[0074] The design of the reactor in the embodiment improves the management of the gases produced during the electrosynthesis process, the pressure can be equalized on the membrane, and the gases can be collected under pressure. The design allows gravity feeding and gravity-assisted product separation, and extends the membrane life by reducing membrane fouling, which is a major problem for membrane reactors using organic matter. The embodiment simplifies the integrated water cooling in close connection with the electrodes, and achieves simple manufacturing, suitable for mass production of the reactor and its products.

[0075] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person familiar with the technical field can easily think of various equivalent modifications or substitutions within the technical scope disclosed by the present invention, and these modifications or substitutions should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention shall be based on the protection scope of the claims.

Claims

1. An electrocatalytic reactor for synthesizing fuels from biomass and its derived molecules, characterized in that The invention comprises an electrolysis unit, an electrolyte circulation unit and a cooling unit, wherein the components arranged in each unit are interconnected, wherein: the electrolysis unit comprises an anode chamber shell, an anode chamber membrane reinforcement sheet, a proton exchange membrane, a cathode chamber membrane reinforcement sheet and a cathode chamber shell, an anode chamber membrane reinforcement sheet and a cathode chamber membrane reinforcement sheet are arranged between the anode chamber shell and the cathode chamber shell, and a proton exchange membrane is arranged between adjacent anode chamber membrane reinforcement sheets and cathode chamber membrane reinforcement sheets; the anode chamber shell and the cathode chamber shell are both divided into two connected chambers by a cooling water tank channel which is recessed inwardly from the outer surface of the shell; the anode chamber shell is used to accommodate the anode electrolyte liquid, and an anode electrode sheet is installed therein; the cathode chamber shell is used to accommodate the cathode electrolyte liquid, and a cathode electrode sheet is installed therein; the electrolysis unit provides direct current to the anode chamber and the cathode chamber respectively through the anode electrode sheet and the cathode electrode sheet, the anode chamber undergoes an oxidation reaction to produce oxygen and protons, the protons reach the cathode chamber through the proton exchange membrane, and the dissolved biomass and its derivative molecules in the cathode chamber undergo an electrochemical hydrogenation reaction, wherein the cooling water tank channel is square, and the cooling water tank channel is connected to the cathode / anode chamber The cathode chamber and the anode chamber surrounded by the shell are inner tanks with square grooves, and the inner tanks are respectively the anode and cathode liquid flow chambers, the cathode and cathode electrolyte inlets are located in the lower half of the side of the inner tank, and the electrolyte outlet is located in the upper half of the side of the inner tank, and the electrolyte inlet and electrolyte outlet of the anode chamber and the cathode chamber are located on both sides of the chamber, and the electrolyte inlet and outlet of the anode chamber and the cathode chamber do not interfere when connected to the outer tube; the protruding position of the middle part of the inner tank of the anode and cathode chambers is provided with parallel strips that are concave outward and have a certain spacing, and the strips are The direction is perpendicular to the axial direction of the cooling water tank channel. The parallel strip belt is installed with anode and cathode electrode sheets. The size range of the electrode sheets is 5-50mm in width, 0.1-3mm in thickness and 50-1250mm in length. The spacing between the electrodes is 3-5cm. A cathode and cathode electrolyte gap layer is reserved between the cathode and cathode electrode sheets and the cathode and cathode chamber membrane reinforcement sheets to allow the electrolyte to pass through. A two-way pressure valve is provided above the cathode and cathode chamber shells, and a drain port is provided below. The two-way pressure valve keeps the pressure on both sides of the membrane at a constant value between 0.4 MPa and 3 MPa. The electrolyte circulation unit includes an electrolyte inlet, an electrolyte outlet and an electrolyte pumping assembly which are arranged on both the anode chamber housing and the cathode chamber housing. The electrolyte pumping assembly connects the electrolyte inlet and the electrolyte outlet in the anode and cathode housings. The electrolyte inlet and the electrolyte outlet come from different chambers separated by cooling water channels in the corresponding housings, so that the electrolyte circulates through the reactor. The cooling device includes a cooling water tank channel which is recessed inwardly on the shell surface of the anode chamber shell and the cathode chamber shell, a cooling water inlet and a cooling water outlet located at both ends of the cooling water tank channel, and an anode cooling water tank cover and a cathode cooling water tank cover located at the upper part of the cooling water tank channel.

2. The electrocatalytic reactor according to claim 1, characterized in that: The electrolyte outlet, electrolyte inlet, cooling water outlet and cooling water inlet on both sides of the cathode chamber and the anode chamber are all designed with threaded openings. When discharge is required, the inlet and outlet can be opened by loosening the sealing bolts; when discharge is not required, the inlet and outlet can be tightly closed by tightening the sealing bolts.

3. The electrocatalytic reactor according to claim 1, characterized in that: The bottom of the anode chamber and the cathode chamber are provided with a labyrinth turbulent structure, so that the anode and cathode liquids generate local reflux in the reaction chamber, thereby improving the uniformity of the liquid in the chamber and prolonging the reaction time of the liquid on the electrode surface.

4. The electrocatalytic reactor according to claim 1, characterized in that: The anode and cathode chamber membrane reinforcement sheets are perforated at positions directly opposite to the cathode and cathode electrolyte gap layers to allow contact with the electrolyte solution.

5. The electrocatalytic reactor according to claim 1, characterized in that: The cooling unit is a unit in which water flows through the reactor channel in close contact with the back of the electrode material. The anode and cathode chamber shells are equipped with thermocouples and electronic thermostats. The temperature of the reactor is monitored according to the settings on the cooler. The thermocouple is used to detect the temperature of the electrolyte solution in the anode and cathode chamber shells. The thermostat is used to control the output power of the chiller according to the temperature detected by the thermocouple, and the temperature of the electrolyte in the cathode chamber is controlled by changing the power of the heating resistor in the cathode chamber.

6. The electrocatalytic reactor according to claim 1, characterized in that: The electrolyte pumping assembly consists of an HPLC peristaltic pump and an electrolyte storage tank located on a pipeline. After the acid hydrolysis product biomolecules in the biomass raw material acid hydrolysis tank are mixed with the cathode electrolyte, the pumping assembly connects the electrolyte inlet of the cathode chamber shell with the electrolyte outlet to move the electrolyte fluid through the reactor, which allows the unreacted biomolecules to enter the electrocatalytic reactor chamber through the inlet and enter the subsequent fractionation and purification tank through the outlet for separation and purification. The electrolyte inlet of the anode chamber is connected to the electrolyte outlet through the anode electrolyte fluid pumping assembly to form a circulation loop.

7. The electrocatalytic reactor according to claim 1, characterized in that: The cathode and anode electrode substrates are made of graphite and coated with catalyst materials, with platinum as the cathode catalyst material and nickel as the anode catalyst material.

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