CN104619886B - The method of Carbon dioxide electrochemical reduction and high surface area electrode - Google Patents

The method of Carbon dioxide electrochemical reduction and high surface area electrode Download PDF

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Publication number
CN104619886B
CN104619886B CN201380048093.9A CN201380048093A CN104619886B CN 104619886 B CN104619886 B CN 104619886B CN 201380048093 A CN201380048093 A CN 201380048093A CN 104619886 B CN104619886 B CN 104619886B
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cathode
alkali metal
catholyte
anode
carbon dioxide
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CN104619886A (en
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杰瑞·J·卡茨
希欧多尔·J·科瑞美
昆塔尔·克夏
保罗·马依斯崔克
兹比格纽·特瓦尔多夫斯基
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Avantium Knowledge Centre BV
Avantium NV
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Afanda Knowledge Centre Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Abstract

It provides for carbon dioxide to be electrochemically transformed to the method and system for the organic product containing formates and formic acid.This method includes but is not limited to step (A) to step (C).Step (A) includes that acid anodolyte is introduced in the first compartment of electrochemical cell, and the first compartment includes anode.Step (B) introduces the catholyte based on bicarbonate containing saturation carbon dioxide in the second compartment of electrochemical cell, and the second compartment includes high surface area cathode, and the cathode includes indium coating and has 30% to 98% void volume.Catholyte of at least part based on sodium bicarbonate is recycled.Step (C) applies a potential between the anode and cathode, it is sufficient to make at least one of carbon dioxide conversion single carbon based products or more carbon-based products.

Description

The method of Carbon dioxide electrochemical reduction and high surface area electrode
Technical field
The present disclosure generally relates to electrochemical reaction fields, more particularly to carry out carbon dioxide electrification by high surface area electrode Learn the method and/or system of reduction.
Background technique
In production activity, such as power generation, transport and production, the burning of fossil fuel can all generate billions of tons every year Carbon dioxide.It is since nineteen seventies studies have shown that the increase of atmospheric carbon dioxide levels can be exactly the whole world The reason of climate change, variation and other potential lethal effects such as ocean pH value.Countries in the world, including the U.S., all just Finding the method for reducing CO2 emission.
It is to economic useful substance, such as fuel and industrial chemical that the mechanism of emission reduction, which is by carbon dioxide conversion,.Such as Fruit uses the energy chemical recycling of carbon dioxide of the renewable sources of energy, reduce the discharge of carbon dioxide and be by renewable energy conversion can be by The chemical form of storage for future use all has can.
Preferred embodiment is summarized
The disclosure produces a carbon (C1) chemicals, including first by using high surface area electrode and special electrolytic solutions Acid, and based on more carbon (C2+) chemicals (i.e. compound contain two or more carbon atoms chemicals).The disclosure includes side Method, system and various compositions.
It should be understood that above-mentioned general description and detailed description below are all that the typical example of the disclosure and an explanation are made Example does not limit the disclosure.In specification and the diagram of part of specification is formed, elaborates the public affairs The specific embodiment opened, and and the common principle for explaining the disclosure of general description.
Brief Description Of Drawings
By reference to following drawings, those skilled in the art are better understood the multiple features of the disclosure:
Fig. 1 is the flow chart of the preferred electrolyzer system of the carbon dioxide reduction described in accordance with an embodiment of the present disclosure；
Fig. 2 is the flow chart of preferred electrochemistry acidification system；
Fig. 3 is the flow chart of the optimum decision system of another Carbon dioxide electrochemical reduction reaction；
Fig. 4 is the flow chart of another preferred electrochemistry acidification system containing Bipolar Membrane；
Fig. 5 is the stream of another electrochemical cell system preferably containing carbon dioxide reduction reaction ion-exchange chamber Cheng Tu；
Fig. 6 is the flow chart according to the nanofiltration system of the disclosure；
Fig. 7 is the cumulative production figure of the formic acid according to the embodiment of the present disclosure 1 at any time；
Fig. 8 is the cumulative production figure of the formic acid according to the embodiment of the present disclosure 2 at any time；
Fig. 9 is the cumulative production figure of the formic acid according to the embodiment of the present disclosure 3 at any time；
Figure 10 is the cumulative production figure of the formic acid according to the embodiment of the present disclosure 4 at any time；
Figure 11 is the cumulative production figure of the formic acid according to the embodiment of the present disclosure 9 at any time；
Figure 12 is the figure of the formic acid concn according to the embodiment of the present disclosure 9 at any time；
Figure 13 is the cumulative production figure of the formic acid according to the embodiment of the present disclosure 10 at any time；
Figure 14 is the figure of the formic acid concn according to the embodiment of the present disclosure 10 at any time；
Figure 15 is the figure of the cell voltage of the operation according to the embodiment of the present disclosure 11 at any time；
Figure 16 is the figure of cathode formic acid concn at any time according to the embodiment of the present disclosure 11；
Figure 17 is the figure of the current efficiency of the formic acid according to the embodiment of the present disclosure 11 at any time；
Figure 18 is the figure of catholyte pH value at any time according to the embodiment of the present disclosure 11；
Figure 19 is the figure of the current efficiency of the formic acid according to the embodiment of the present disclosure 12 at any time；
Figure 20 is the figure of catholyte formic acid concn at any time according to the embodiment of the present disclosure 12；With
Figure 21 is the figure of catholyte pH value at any time according to the embodiment of the present disclosure 12.
Preferably embodiment is specifically described in detail
The existing preferred embodiment of the disclosure will be discussed in detail now, the embodiment in embodiment passes through attached drawing It illustrates.
According to some embodiments of the disclosure, providing carbon dioxide conversion is the organic production for including formates and formic acid The electro-chemical systems of object.Promote the process with the three-dimensional material electrode of high surface area, acid anodolyte and catholyte.
Before explaining in detail any embodiment of the disclosure, it is understood that following embodiments cannot be limited and be connect The scope of the claims got off.Likewise, it should also be appreciated that being for illustrative purposes for wording used herein and term And it should not be construed as limiting.The application of term, as "comprising", " Consists of " or " having " and various change are all meaned Include the content listed thereafter and equivalent wherein the same with addition Item.Further, unless otherwise noted, skill Art term is used according to conventional use.
Referring to Fig. 1, for the flow chart with the electrolyzer system 100 of embodiment of the present invention, electrolyzer system 100 can be with It is used for Carbon dioxide electrochemical reduction reaction and generates organic product or organic product intermediate.Preferably, electrolyzer system 100 Reduce the alkali metal formate of carbon dioxide conversion imaging potassium formate.Electrolyzer system 100 generally comprises electrolytic cell 102, sun Pole liquid circulation loop 104 and catholyte circulation loop 106.Electrolyzer system 100 may include as raw material method/it is defeated Enter carbon dioxide, catholyte contain sodium bicarbonate (potassium bicarbonate, but in addition to saleratus, it is other to be based on bicarbonate Salt compound it is also contemplated that), and acid anodolyte (preferably sulfuric acid, but in addition to sulfuric acid may also comprise other acid).It should The product of electrolyzer system 100 is typically all alkali metal formate, such as potassium formate, and may include excessive electrolyte, dioxy Change carbon, hydrogen, oxygen and/or other unreacted process inputs.
Electrolytic cell 102 generally comprises anode chamber 108 and cathode chamber 110, and can further comprise by anode chamber 108 and cathode The cation-exchange membrane 112 that room 110 separates.Anode chamber 108 includes the anode 114 suitable for aoxidizing water.It is preferred real at one It applies in scheme, anode 114 is that have anode electrocatalyst coating and the Ni―Ti anode towards cation-exchange membrane 112.For example, anode 114 include containing the anode screen 116 for folding expansion titanium net anode elctro-catalyst coating.Anode screen 116 can be in anode 114 Space and contact pressure are provided between cation-exchange membrane 112.Anode 114 also may include one or more on the back side Electric current binding post (not shown).
Cathode chamber 110 generally comprises the cathode 118 to set within it.Cathode 118 preferably includes metal electrode, has in yin Active electrocatalyst layers in the front surface of pole 118, towards cation-exchange membrane 112, and can cathode 118 the back side be arranged one Or multiple current conduction column (not shown).Cathode 118 preferably comprises high surface area cathode construction 120.High surface area cathode construction 120 are mounted between cation-exchange membrane 112 and cathode 118, with conduct electric current to high surface area cathode construction 120.In height Interface between surface area cathode construction 120 and cation-exchange membrane 112 includes insulation screen (not shown), such as thin plastic foamed Net insulation screen is minimized with the directly contact between high surface area cathode construction 120 and cation-exchange membrane 112.
Anode chamber 108 generally includes the anode feed stream 122 containing diluted acid electrolyte solution.Anode feed stream 122 can lead to It crosses a face of anode 114 and flows into the bottom of anode chamber 108 by anode network 116.Reaction in anode chamber 108 can wrap It includes and generates oxygen (O2, that is, gaseous oxygen) and hydrogen ion (H+) or water in the proton for applying electric current and oxidation at voltages and generating.Hydrogen from Son or proton can generally be obtained by cation-exchange membrane 112 in the reaction of cathode chamber 110.Gaseous oxygen and other liquid conducts Anode export stream 124 leaves the anode chamber 108 of electrolytic cell 102.Anode export stream 124 can be monitored simultaneously by temperature sensor 126a And the anode decoupler 128 that flow direction is suitable for separating oxygen from anode export stream 124.Anode decoupler 128 can will be positive Pole outlet stream 124 brings oxygen stream 130, anode liquid recycle stream 132 and anodolyte overflow stream 134 into.Oxygen stream 130 can be from Anode decoupler 128 is discharged.Anode liquid stream 132 can be with the water (preferably deionized water) from water source 136 and the acid from acid source 138 (preferably sulfuric acid) combines.Water source 136 and acid source 138 in anolyte circulation loop 104 are able to maintain that anode feed stream 122 Acid strength and volume.The temperature of anode feed stream 122 can be before the anode chamber 108 for entering electrolytic cell 102 by being connected with The heat exchanger 140a of cooling water source 142a is adjusted.
Cathode chamber 110 generally comprises the cathode feed flow 144 containing carbon dioxide and catholyte.It is preferred real at one It applies in scheme, cathode is the bicarbonate compound of carbon dioxide saturation, such as saleratus (KHCO3).Cathode feed flow 144 can To flow into the bottom of cathode chamber 110 by the one side of cathode 118 and by the cathode construction 120 of high surface area.Cathode chamber It is formic acid that 110 reaction can reduce carbon dioxide conversion under the electric current and voltage of application.Reaction product and any unreacted Material (such as excessive catholyte solution) can exit cathode chamber 110 as cathode outlet stream 146.Cathode outlet stream 146 It can be monitored by pH sensor 148a and temperature sensor 126b and flow to one and be suitable for gas componant (such as hydrogen Gas) the anode decoupler 150 separated from anode export stream 146.Anode decoupler 150 can be by 146 band of anode export stream Enter hydrogen stream 152, product stream 154 and catholyte recycle stream 156.Hydrogen stream 152 can be discharged from anode decoupler 150. Product stream 154 preferably comprises alkali metal formate (such as potassium formate electrolyte containing saleratus) and may include extra yin Pole.Cathode liquid stream 156 can be handled by the heat exchanger 140b of catholyte circulating pump 158 and connection cooling water source 142b. One new catholyte supply 160 is measurable to enter cathode liquid stream 156, the new catholyte in cathode liquid stream 156 The pH value of the cathode feeding flow 144 of the adjustable cathode chamber 110 into electrolytic cell 102 of supply 160, can control final production in this way The flood rate of object and the concentration for establishing carboxylic acid product.PH value can be monitored by pH sensor 148b.One comes from catholyte The metering before the cathode chamber 110 for entering electrolytic cell 102 of the carbon dioxide stream 162 of supply 160 is sent under cathode feed flow 144 Trip.Preferably, the saturation catholyte of carbon dioxide enters cathode chamber.
When entering the acid anodolyte of cathode chamber by film using the proton in acid anodolyte, electrolytic cell 102 pH value can be controlled or be maintained by using the alkali metal hydrogencarbonate in conjunction with water and/or in conjunction with the carbonate of water to control The pH value of catholyte processed.By the pH value of control catholyte in an optimum value, catholyte can be not kept at optimal than it PH value or without using pH control mechanism that carbon dioxide is effectively converted into higher conversion ratio the product of C1 and C2.? During one preferred, catholyte constantly recycles to keep enough and uniform two in the cathode surface containing elctro-catalyst Carbonoxide.One new catholyte feeding flow can be used for controlling catholyte pH value and control the overflow production concentration in product.Yin Preferentially balance and proton divide in cathode in cathode the mass flow (for example, mass flow of potassium carbonate) of the cathode charging of pole room The byproduct reaction of the inefficiency of Xie Shui forms hydroxide.The concentration of saleratus is important, because it is provided to cathode, This will be diluted in the product of cathode.
The pH value of potassium bicarbonate control catholyte, wherein the concentration range of saleratus is 5 to 600gm/L, Or more preferably in the range of 10 to 500gm/L.If catholyte input concentration is fixed, independent feed water can be applied to yin The concentration of pole hydraulic control final product.In another embodiment, potassium carbonate can be used for the control charging of pH value.Potassium carbonate is in water There is higher solubility than saleratus, and preferred concentration range is 5 to 1500gm/L.
It referring to fig. 2, is a kind of block diagram of electrochemistry acidification system 200 described in the embodiment of the present invention.Electrochemistry acidification system System 200 can be used for being acidified the product stream 154 from electrolyzer system 100.Preferably, 200 acidizing alkali of electrochemistry acidification system gold Belong to formates, such as potassium formate to form organic acid, and cooperates with generation alkali metal hydroxide, such as potassium hydroxide.Electrochemistry acidification System 200 generally comprises electrochemical acid electrochemical cell 202, anodolyte circulation loop 204 and catholyte circulation loop 206.Electrochemistry acidification system 200 may include method/input as raw material from 100 product stream 154 of electrolyzer system The water of (preferably comprising alkali metal formate), each anodolyte circulation loop 204 and catholyte circulation loop 206 and Acid anodolyte (preferably sulfuric acid, but in addition to sulfuric acid also may include other acid).200 product of electrochemistry acidification system is logical It is often organic acid, such as formic acid and alkali metal hydroxide, and may include remaining alkali metal formate, bicarbonate electrolysis The input of matter, carbon dioxide, hydrogen, oxygen and/or other reaction process.
Electrochemical acid electrochemical cell 202 is preferably the electrochemistry acidification unit or battery of three compartments.Electrochemical acid electrochemical cell 202 Anode chamber 208, cathode chamber 210 are generally comprised, and is exchanged by the central ion on two boundary cation-exchange membrane 214a and 214b Room 212.Anode chamber 208 includes the anode 216 suitable for aoxidizing water.In a preferred embodiment, anode 216 is to face The Ni―Ti anode with anode electrocatalyst coating of cation-exchange membrane 214a.Cathode chamber 210 includes being suitable for reducing water and life At the cathode 218 of alkali metal hydroxide.In a preferred embodiment, electrochemical acid electrochemical cell 202 is in potential and electric current Under the action of anode chamber 208 can generate hydrogen ion (H+) or proton.Hydrogen ion (H+) or proton pass through cation-exchange membrane 214a Into central ion switch room 212.Product stream 154 from electrolyzer system 100 preferably passes through central ion switch room 212 It is introduced into electrochemical acid electrochemical cell 202, the hydrogen ion (H in electrochemical acid electrochemical cell 202+) or proton instead of product stream Alkali metal ion (for example, potassium ion) in 154 contains organic acid product (preferably formic acid) to be acidified the product stream and generate Product stream 260.Free alkali metal ion enters going back with the water of cathode in cathode chamber 210 by cation-exchange membrane 214b Hydroxide ion (the OH generated in original reaction-) combine to form alkali metal hydroxide, preferentially generate potassium hydroxide.
Central ion switch room 212 is containing plastics gauze pad (not shown) between cation-exchange membrane 214a and 214b Central ion switch room 212 keeps dimension space.In one embodiment, cationic ion exchange material 220 be included in sun from In central ion switch room 212 between proton exchange 214a and cation-exchange membrane 214b.Cation exchange material 220 can wrap It includes with the ion exchange resin of pearl, fiber or other forms.It is contemplated that the cation exchange material 220 can increase from Sub- switch room's electrical conductivity of solution, and can reduce when carbon dioxide gas forms bubble to the latent effect of cell voltage and pass through Heart ion-exchange chamber 212.
Anode chamber 208 generally includes the anode feed stream 222 (preferably sulfuric acid solution) containing acid Anolyte solution. The gaseous oxygen and other liquid for leaving anode chamber 208 as anode export stream 224 leave electrochemical acid electrochemical cell 202.Anode goes out Mouth stream 224, which is monitored by temperature sensor 226a and can flow to the anolyte for being suitable for separating oxygen from anode export stream 224, to break Open device 228.Anode export stream 224 can be sent into oxygen stream 230, anode liquid recycle stream 232 and anode electricity by anolyte decoupler 228 Solve matter overflow stream 234.Oxygen stream 230 can be discharged from anolyte decoupler 228.Anode liquid stream 232 is understood and comes from water source 236 Water (preferably deionized water) and acid (preferably sulfuric acid) from acid source 238 combine.Water in anolyte circulation loop 204 Source 236 and acid source 238 can maintain the intensity and quantity of the acid in anode feed stream 222.Anode feed stream 222 is entering electrochemistry Temperature before being acidified the anode chamber 208 of battery 202 can be adjusted by the heat exchanger 240a containing cooling water source 242a Section.
Cathode chamber 210 generally comprises the catholyte feeding flow 244 containing water, and may include by catholyte circulation loop The alkali metal hydroxide of 206 circulations.Reaction product containing alkali metal hydroxide and hydrogen can be used as cathode stream 246 and move back Cathode chamber 210 out.Cathode outlet stream 246, which can be monitored by temperature sensor 226b and can flow to one, to be suitable for from yin In the cathode decoupler 248 of 246 separates gas components of pole outlet stream (for example, hydrogen).Cathode decoupler 248 can be by cathode outlet stream 24 successively become hydrogen stream 250, catholyte mass flow 252 and catholyte overflow stream 254, wherein may include KOH.Hydrogen stream 250 can discharge from cathode decoupler 248.Cathode liquid stream 252 preferably includes alkali metal hydroxide and (such as is containing potassium formate Steam product 154 in potassium hydroxide).Cathode liquid stream 252 can by catholyte circulating pump 256 and contain cooling water source 242b Heat exchanger 240b processed.Temperature sensor 226c can monitor the cathode stream 252 for coming the downstream automatic heat-exchanger 240b. Cathode liquid stream 252 can be combined with the water (preferably deionized water) from water source 258, and the water at water source 258 is for measuring control System enters the concentration of the alkali metal hydroxide of the catholyte feeding flow 244 of cathode chamber 210.
Referring to Fig. 3, for for the flow chart by Carbon dioxide electrochemical reduction at the optimum decision system 300 of organic acid product. System 300 includes electrolyzer system 100 (described referring to Fig.1) and electrochemistry acidification system 200 (referring to described in Fig. 2), and excellent Choosing includes a potassium hydroxide recirculation circuit 302 suitable for producing potassium hydroxide from saleratus and carbon dioxide.System System 300 also includes separation (for example, gas separate tank 304a, 304b, 304,304d) and the process stream of carbon dioxide treatment component The recycling of middle carbon dioxide.
System 300 generally comprises carbon dioxide, alkali metal hydroxide (preferably potassium hydroxide), sour (preferably sulfuric acid), makees Output for the water (preferably deionized water) of the input of process and as process usually contains organic acid (preferably formic acid), oxygen The water of gas and hydrogen.Organic acid can carry out additional processing to provide required form and concentration.Such processing may include Evaporation, distillation or other suitable physical separation/enrichment process.
The chemical reduction reaction process of carbon dioxide can be as follows in system 300.
Hydrogen chemisorption is on the electrode in the reduction reaction of water, as shown in reaction equation (1).
H++e-→Had (1)
Carbon dioxide and the hydrogen atom of absorption restore to form formates in cathode surface, as shown in reaction equation (2).
CO2+Had→HCOOad (2)
It is adsorbed on formic acid on cathode surface and then forms formic acid with the hydrogen atom of another absorption, and be released in solution, As shown in reaction equation (3).
HCOOad+Had→HCOOH (3)
Hydrogen and hydroxide ion are formed in the reduction reaction that the competitive reaction of cathode is water, as shown in reaction equation (4).
2H2O+2e-→H2+2OH- (4)
It is and hydrogen ion by water oxygen oxygen in the reaction of anode, as shown in reaction equation (5).
2H2O→4H++4e-+O2 (5)
The cathode of high surface area
According to Fig. 1, cathode 118 is preferably with the cathode construction 120 of high surface area.The cathode construction of high surface area 120 preferably include the void volume of the range from 30% to 98%.The specific surface area of the cathode construction 120 of high surface area preferably from 2 square centimeters/cubic centimetre to 500 square centimeters/cubic centimetre are higher.This surface region can also be with more preferably 2x to 1000x or more high scope are defined as the gross area compared with distributing switch/conductor plate.
Cathode 118 preferably includes to be coated with copper mesh grid, copper mesh, copper fiber and bronze and other copper-tin alloys, nickel and not Tin (Sn) electroless plating indium of rust steel.These metals can coat other metals in advance, to be sufficiently formed indium and other preferred cathodes The suitable applications basis of coating.Cathode can also include the indium-formed on the surface of copper fiber, mesh grid, foam copper or copper mesh Compound between copper metal.Intermetallic compound is usually harder than soft metal indium, and can provide the reason other than catalytic performance can be used The mechanical performance thought.Cathode further include but be not limited only to comprising lead, tin, mercury, thallium, indium, bismuth and cadmium and their alloy and The coating and/or metal structure of their combination.Metal includes titanium, niobium, chromium, molybdenum, silver, cadmium, mercury, thallium, An and Pb and chromium Ni-Mo alloy steel etc. can merge.Cathode 118 may include single-layer or multi-layer electrode coating, it may for example comprise one or more layers gold Belong to the catalyst coat with the cathode base of alloy.Preferred electrocatalyst for cathode coating includes being coated in high surface area and top It is coated with the tin of the copper base of indium layer.The covering of indium coating is preferably as indium range from 5% to 100%.
The catalytic surface of electrode exposure indium alloy in use, indium and other metals in indium compositions preferred alloy For range from 5% to 99%, other metals include tin, lead, mercury, thallium, bismuth, copper, cadmium and their composite alloy and combinations thereof.Also it answers It includes Au, Ag, Zn and the Pd of percentage range from 1% to 95% in coating that this, which is contemplated to,.
In addition, metal oxide can be used as the elctro-catalyst on basic cathode construction surface.For example, the oxidation of lead Object can be used as the elctro-catalyst on basic cathode construction surface.Coating of metal oxides can be by according to chemical action or thermal oxide The thermal oxidation method or electrodeposition process of effect are formed.
In addition, cathode foundation structure is also gradual change, for example, the concentration of cathode is with regard to dense on horizontal or vertical direction It can be for degree, voidage or specific surface area (such as different fiber sizes) a variety of.Cathode construction further includes two Or more different carbon monoxide-olefin polymerics, these different carbon monoxide-olefin polymerics be blended in or positioned at cathode chamber cathode construction Independent region in.
It, will be in the loss and catalysis of catalyst with regard to the formate yield of system performance in the normal operation of electrolytic cell 102 Agent coating contains impurity and reduces, such as other metals can be plated on cathode 118.The surface of cathode 118 can be electrolysed Indium salts or mixed indium/tin original position salt in the operation of slot 102 update.According to 118 structure of cathode, we can predict other or volume Outer metal salt can be added in situ alone or in combination, these salt include Ag, Au, Mo, Cd, Sn and other suitable metals Salt.Electrolytic cell 102 at runtime can be with full speed running, or temporarily adds or be not added any carbon dioxide during injection of metallic salt Low concentration stream in work.These the additional salt of surface for updating cathode under the above conditions will be according to needing to update different knots Fruit.The use of reverse current of short duration once in a while can also be used to update cathode surface during the operation of electrochemical cell.
In specific embodiments, electrolytic cell 102 is run under superatmospheric pressure, this can lead to higher Current efficiency, allow for electrolytic cell 102 than be located at or subatmospheric power under run when can be in higher current concentration Lower operation.
When preparing the cathode material of organic chemicals production, in the reducible metal salt of cathode construction surface addition It can be used, the Ag, Au, Mo being such as added, Cd, Sn and other suitable metal.Such addition metal salt, which can provide, urges Change surface, otherwise such catalytic surface would become hard to directly prepare in cathode preparation or the update of catalytic surface.
The preferred method for preparing the cathode construction 120 of high surface area is using chemical plating fluid, and this chemical plating fluid includes indium Salt, at least one complexing agent, reducing agent, pH adjusting agent and surfactant.Electrolysis indium coating is formed in the cathode of high surface area Preferred method includes that following material: Trisodium citrate dihydrate (100g/L), ethylenediamine is combined in the deionized water of stirring Tetraacethyl disodium (15g/L), sodium acetate (10g/L), indium trichloride (anhydrous, 10g/L) and thiodiglycolic acid (0.3g/L, example Such as, the solution of the 100mg/ml of 3ml).Stirred premix deposition solution (preferably multiple hours, such as overnight) can also To be used.The process further includes heating the mixture to about 40 DEG C.The program further includes 40 milliliters of TiCl of addition3(2%HCl Middle 20wt.%) every liter [0.05mM] and 7M ammonium hydroxide is added into methanol until the pH value of mixture (the about 15mL ammonium hydroxide/every that are about 7 Rise), at this point, ammonium hydroxide (28% ammonia spirit) is used to adjust pH value between about 9 and 9.2.Then the process Including heating the mixture to about 60 DEG C.If pH value declines, pH value is adjusted to about 9 with Ammonia.Then the mistake Journey includes heating the mixture to about 75 DEG C, starts deposit occur at about 65 DEG C.The process includes keeping mixture In 75 DEG C of about hours.
The preferred method of the metal coating of copper base includes cleaning the copper surface of naked copper substrate in acetone (such as to remove copper removal Oil or lubricating grease remained on surface), the copper base then crossed in deionized water cleaning with acetone treatment.The process further include by Naked copper substrate is put into 10% sulfuric acid bath about 5 minutes, is then cleaned with deionized water.The process further includes the table in copper The tin of face setting about 25um.Deposition process can be by using business electrolytic tinning liquid (Caswell, Inc.) to continue at 60 DEG C It 15 minutes realizes.When tin deposition, each section is also thoroughly cleaned in deionized water.The process further includes being coated with The copper surface of tin deposits about 1 μm of indium.The deposition process is by operating 60 minutes in electrolytic cell at a temperature of 90 °C bath come real It is existing.With the deposition of indium, each section is thoroughly cleaned in ionized water.The process further includes being put into plated copper/tin/indium copper 5 minutes in the nitric acid bath of 5wt%.Compared to the stabilization that electrode can be improved in processing as untreated copper/tin/indium electrode Property.In another embodiment, electrolytic tinning copper base, which can be placed into molten indium, carries out coating.
In the particular embodiment, cathode base will be used as the catalysis material of carbon dioxide reduction reaction.It is four as follows A Processing Example.
The first processing includes the electric conductivity base in the high activity surface area of the generation containing enough catalyst materials Signa Gel (for example, vitreous carbon or metal) is coated on plate.The conducting element of gel has catalytic activity.With the colloidal sol-of catalysis For gel by after substrates coatings, sol-gel can be carried out the polymerized/cross-linked of height.Composite substrate/sol-gel structures exist It is under high temperature that organic material is converting at amorphous carbon (potential electric conductivity).Hot formal similarity can also carry out selectively The chemical treatment for removing organic material or silicon phase, obtains the high coating of catalyst content.
Second of processing includes use as adhesive amido, adhesive mercaptan are relatively small (such as micron or nanoscale) Particle or other suitable adhesives.Adhesive preferably can be conductive between electrically-conductive backing plate and catalyst granules.Catalyst Particle preferably comprises conjugated organic molecule.If substrate is also to be made of catalyst material, adhesive is just had symmetrically Conjugated group, otherwise we can using containing there are two different conjugated groups binder.
The third processing include by substrate the slurries floating coat (form that can be salt) containing catalyst material and glue Tie agent.Slurry can also contain conductive agent, such as carbon black, carbon nanotube or other suitable conductive additives.Then coating paste It will be attached on substrate by drying to form a conformal coating.Substrate and dry slurry are heated so as to various groups and become a useful person Material has mechanical robustness, electric conductivity and material catalytic.In a specific embodiment, substrate and dried slurry Heating appears in reducing environment.
4th kind of processing mode includes by the precursor of application substrate, removal solvent and baking substrate, by precursor material Monolithic semiconductor metal chalcogenide coating metal chalcogenide compound semiconductor substrates coatings.These coating materials include But it is not limited only to Na4SnS4、Na4Sn2S6、K4SnTe4、Na3AsS3、(NH4)4Sn2S6、(NH4)3AsS3(NH4)2MoS4。
The technology of preparing of other coatings and elctro-catalyst includes the thermal oxide being applied on substrate, and formation contains substrate Semiconductor material is simultaneously applied on substrate by intermetallic compound.In one embodiment, the metal salt of various thermal oxides applies It is the first choice of the high surface area material of the electrochemical reduction suitable for carbon dioxide to various metals and ceramic substrate.Thermal oxide with It is similar that the anode material that catalyst is used as in electrochemistry chloride cell is formed on titanium, such as yttrium oxide and ruthenium-oxide. In another embodiment, then copper foil is heated to 40 DEG C of indium fusing point or more, until metal foil by the indium plating on copper foil The indium on surface melts the golden metallic copper of shape, is then cooled down.The formation of intermetallic compound can be in air or inertia Gas (such as argon gas or helium) carries out under all or part of vacuum atmosphere.Plated material preferably provides about 50% farad Transfer efficiency, and the coating of planar metal plate and copper fiber can be used as.Intermetallic compound can also with it is tin plating Copper base forms one.In another embodiment, semiconductor material can be by by being vapor-deposited, sputtering or other suitable Application method be applied on substrate.The preferred metal substrate of substrate.Semiconductor material can be the required P-type or N- of doping Type.
In the 4th kind of processing mode and the coating technology of other foregoing descriptions, specific measure be used to improve substrate and The quality (mechanical, electrically, etc.) of the linkage of catalyst.These measures can be related to function of creation group on substrate, these function bases Group can carry out the chemical bond with catalyst or binder, or in substrate surface, convenient for applying catalyst coat combination geometry spy The creation of sign.
The cathode of the high surface area may include RVC material, and if carbon and graphite, foam metal, gold net belong to, fiber is made Metal wool, powder sintered metal film and plate, metal and ceramic particle, ball, ceramics and metal column and trickle bed packing timber Material, metal and inorganic powder form, metallic fiber and woollen or other suitable baseplate materials.The specific surface area of physical form is excellent Choosing is 2 to 2000cm containing specific surface area2/cm3Or it is bigger.
The high surface area structure of electrode or electrode can carry out alloy with fiber or woollen, can coat various chemical combination Object then burns in air or in reducing atmosphere furnace, and the surface of the carbon dioxide reduction in electro-catalysis forms stable Oxide.Other cathode materials may include glassy metal and amorphous metal.
It is that the scheme of particular implementation acidification system 200 shown in Fig. 2 is double in electrochemical acid electrochemical cell 402 with reference to Fig. 4 The concrete application of Polar Crystal Slab.Alkali metal first by the application of 402 Bipolar Membrane of electrochemical acid electrochemical cell, in addition to recycling potassium hydroxide Hydrochlorate (such as potassium formate) can be acidified.Voltage required for the formic acid that the use of Bipolar Membrane can reduce alkali metal is acidified, and The quantity of the actually required anode and cathode of electrochemistry heap can be reduced.Cation of the Bipolar Membrane preferably by being bonded together Exchange membrane and anionic membrane are constituted, and are worked by decomposing water in two membrane interfaces, form hydrogen ion (H from cationic membrane+) and from Anion-exchange membrane forms hydroxide ion (OH-)。
It is that Fig. 1 illustrates another embodiment of electro-chemical systems 100 with reference to Fig. 5.Electrolytic cell 502 in Fig. 5 is in addition to sun Pole room 506 and cathode chamber 508, including ion-exchange chamber 504.The function of the ion-exchange chamber 504 is the same as electrochemical acid shown in Fig. 2 The acidification room 212 of electrochemical cell is similar.Alkali metal formate product (such as potassium formate) and unreacted carbonic acid from cathode chamber Hydrogen potassium is provided by ion-exchange chamber 504 containing CO2With the carboxylic acid product of some remaining saleratus.Hydrogen ion (H+) logical It crosses in anode chamber side adjacent membranes 510a instead of the alkali metal ion flowed by central ion switch room 504 (for example, K+), it is above-mentioned So that alkali metal formate is acidified and alkali metal ion and remaining hydrogen ion are entered by cathode chamber 508 and adjacent film Cathode 510b.If cathode can be in higher pH it is required that the cathode of the process of selection obtains high faradaic efficiency Under the conditions of operated.
In the cathod system based on indium, preferred catholyte includes alkali metal hydrogencarbonate, carbonate, sulfate With phosphate etc..Other preferred catholytes include borate, ammonium and hydroxide.Other catholytes can wrap Include chloride, bromide and other organic salts and inorganic salts.Nonaqueous electrolyte, as propene carbonate, methane sulfonic acid, methanol and its Its ionic conduction liquid can be used, these nonaqueous electrolytes can be in the mixture of water, or as in catholyte Non-aqueous mixtures.Carbon dioxide is introduced in a manner of microbubble in cathode liquid stream can improve carbon dioxide to cathode surface Conveying.
Referring now to Figure 6, nanofiltration system can be in electrolyzer system 100 as shown in Figure 1 and electrification as shown in Figure 2 It learns and is used between acidification system 200.Nanofiltration system is preferentially for from leaving electrolyzer system 100 (for example, stream 154) Bicarbonate in separate alkali metal formate (for example, potassium formate), in order to reduce and enter electrochemical acid electrochemical cell The amount of the bicarbonate radical of amount 202.Nanofiltration system is under stress preferentially using nanofiltration membrane/filter from alkali metal formate The separation sodium bicarbonate of selectivity.Nanofiltration/film uses high-pressure pump and the separation UF membrane suitable for selecting from dianion (such as carbonate) isolates univalent anion (such as formic acid).When electrolyzer system 100 and electrochemistry acidification system 200 it Between when using nanofiltration system as separating tool, the sodium bicarbonate (for example, stream 154) in formic acid/bicarbonate is preferably It is in order to effectively from the carbonate separating formic containing nano-filtration membrane that ground, which is converted into carbonate,.Nanofiltration system includes one A frequency mixer, such as blending tank mix formates/bicarbonate product stream and potassium hydroxide (KOH) stream.Mixer Saleratus can be promoted to be converted to potassium carbonate to promote formic acid to come from carbonate separation.High-pressure pump is by potassium formate/carbonic ester It streams into nano-filtration unit, this nano-filtration unit includes nanofiltration/film.Nano-filtration unit produces one containing first The osmotic flow of the low carbon acid of sour potassium, this strand of osmotic flow are then fed in electrochemistry acidification system 200 as shown in Figure 2 as liquid Stream 15 enters electrochemical acid electrochemical cell 202.Potassium carbonate containing the discharge stream for leaving nano-filtration unit is preferentially fed to In the saleratus block of Fig. 3, potassium carbonate and KOH and CO in saleratus block2In conjunction with being converted into saleratus.Saleratus is excellent The first charging as the cathode chamber of the electrolytic cell 102 of electrolyzer system 100.Nanofiltration separation system is a series of including being connected to Multiple units of process configuration separate the gross efficiency of carbonate to increase from formic acid.The system can also be realized using recycle stream The circulation of the input of another battery is flowed to keep flow and pressure from a battery output and improves the recycling of formic acid.
According to the electro-chemical systems, the preferred scope of the pH value of cathode is 3 to 12.The pH value of required catholyte can It is the operating condition of cathode and the function of catalyst, so as to have in electrochemical cell limited or corrosion-free.
The range of the flow of the cross section of preferred cathode is 2 to 3000gpm/ft2(0.0076 arrives 11.36m3/m2) or more Greatly, flow rates arrive 20ft/sec (0.0006 to 6.1 meter per second) for 0.002.
Homogeneity heterocyclic catalyst is preferably used to cathode.Homogeneity heterocyclic catalyst includes, for example, one or more 4- hydroxyl Pyridine, sulfur heterocyclic ring amine, oxygen heterocycle amine, azoles, benzimidazole, bipyridyl, furans, imidazoles, at least contains one five at adenine The imidazoles associated class of member ring, indoles, methylimidazole, picoline, oxazole, Phen, pterin, pteridine, pyridine, at least one Pyridine associated class, pyrroles, quinoline or the thiazole and their mixture of a hexatomic ring.
The preferred anolyte of system includes the hydroxide of alkali metal, such as NaOH, KOH, LiOH；Ammonium hydroxide；Nothing Machine acid, such as sulfuric acid, phosphoric acid etc.；Organic acid, such as methanesulfonic acid；Non-aqueous solution and aqueous solution；Alkali halide salts, such as chlorination Object, bromide and iodide, such as sodium chloride, sodium bromide, lithium bromide and sodium iodide；Acid halide such as HCl, HBr and HI.It is acid Halide and alkali halide salts can generate the water of such as chlorine, bromine or iodine as halide gas or dissolution from anode chamber Product.The on-aqueous liquid of methanol or other hydro carbons can also be used, and having for some oxidations can be formed from anodolyte Machine product.It will be determined by the process of chemical product and requirement to reduce the selection for the cell voltage anolyte integrally runed.Example Such as, the formation of bromine needs a significantly lower anode voltage and lower with the ratio bromine of iodine than the formation of chlorine on anode. This can be saved having significant power in the operation of two electrochemical appliances when generating bromine in anolyte.Halogen It is formed, such as the bromine in anolyte, can be used for producing the external reaction of other compounds, to form bromoethane as alkanes reacts, so After can be converted into alcohol, such as ethyl alcohol or alkene, such as ethylene, and electrochemistry can be recovered to from the by-product of the halogen acids of reaction The anode of battery.The by-product for carrying out self-reacting halogen acids can be recovered to the anode of electrochemical cell.
The electric tank cathode liquor ratio run under higher operating pressure can make more dioxies at lower pressures Change carbon dissolution in aqueous solution (for example, environmental pressure).Electrochemical cell can be up to about the mostly electric of 20 to 30 gauge pressures in pressure Work in the design of pond group heap, although they can be in up to 100psig along with modification.Anode electrolytic cell liquid can also be identical Pressure limit in operation, with reduce to separation two electrodes film pressure difference.Special electrochemistry design is needed higher It is run under 60 to 100 atmospheric pressure or higher atmospheric pressure.This is in liquid CO2And supercritical CO2Opereating specification.
In specific embodiments, the limitation of the flowing with back-pressure can be used in a part of catholyte recycle stream Or pressurizeed respectively using pump using carbon dioxide injection, such pressurized stream will be by the cathode chamber of injection electrolytic cell. Such structure will increase the solubility of carbon dioxide in aqueous solution and then improve conversion ratio.
The operating temperature range of catholyte and anolyte is preferably from -10 DEG C to 95 DEG C, and 5 DEG C to 60 DEG C of better choice.Most Low operating temperature by be restricted to using electrolyte and their freezing point.Carbon dioxide is molten in the aqueous solution of electrolyte Xie Du is just higher.And it will be helpful to obtain higher conversion ratio and current efficiency.The considerations of lower operation temperature is operation The voltage of slot is higher, this is because just needing with the best approach of the production of chemicals of minimum operation expense.
The design of electrochemical cell may include zero clearance, by the catholyte of the cathode material by various high surfaces The design of matter circulation.Other designs include: flood fair current filler and with the trickle bed of the cathode materials of various high surface areas design, The design of bipolar laminated battery design and high-tension battery.
Anode for electro-chemical systems can be dependent on different system conditions.Acid anode and water oxygenization are generated Oxygen and hydrogen ion, anode contain coating, the electro-catalytic coating comprising preferred metal oxide containing precious metals, such as ruthenium and iridium oxide, And platinum, rhodium, gold and their metal combination and the deposition on valve metal substrate oxide, such as titanium, tantalum, zirconium, niobium.It is right In other electrolyte, such as alkalinity or hydroxide electrolyte, anode include carbon, cobalt/cobalt oxide, stainless steel, nickel and they Alloy and can be used as composition existing for anodic stabilization under alkaline condition.
As described herein, the film between anode chamber and cathode chamber can be used in electro-chemical systems.Preferred ion exchange membrane, Especially those anion rejections with higher, such as rely on the perfluorinated sulfonic acid of amberplex, these ion exchanges Film such as DuPontBoard do not reinforce type N117 and N120 series, the N324 of the PTFE fiber more preferably enhanced and N424 type, and such as with Japanese enterprises supplier product nameThe film of lower production is similar.Other application is in chlorine The double-layer structure that the multi-layer perfluor amberplex of alkali industry has base to be bonded to base membrane layer carboxylic acid sulfonic acid film layer, it and anolyte and Catholyte effectively operates under the conditions of pH value is about 2 or is higher.These films have the rejection of higher anion.This It is all the trademark Soynatto of Du Pont oneself a bitN900 series, such as N90209, N966, N982 and 2000 series, such as N2010, N2020 and N2030 and their all types and subclass.If the rejection of anion does not reach critical, that The film based on hydrocarbon being made of different kinds of ions exchange material can also be used, such as those are containing nation's trade names Under by Sybron sell,AGC engineering (Asahi Glass) and moral mountain soda under trade names and in market Upper available other types.
Design of electrolysis cells embodiment
The design of electrolytic cell can be by using the interval frame of addition with the high surface area containing various thickness in laboratory Cathode construction, and the physical contact pressure for being in electrical contact to cathode current conductor substrate is provided.
It is about 108cm containing projected area2The electrochemistry experiment bench battery of electrode be used for many of experiment porch Test case.Electrochemical cell is made of two electrode chambers, the two electrode chambers are from natural from 1.0 inches (2.54 centimetres) thick Processing obtains in polypropylene.The external dimensions of anode and cathode room is 8 inches (20.32 centimetres) to 5 inches (12.70 centimetres), It is the recess portion of 0.375 inch (0.9525cm) containing inside machining depth, it is 3 inches (7.62cm) wide, it is 6 inches (15.24cm) high With 1.0 inches (2.52cm) wide planar pad sealing areas.Two holes for being evenly arranged on concave region accommodate two electrode conductor columns simultaneously By the whole thickness of compartment, and there are two 0.25 inch (0.635cm) of drillings and tapping hole to accommodate plastic fittings, should Plastic fittings prevents the liquid from electrode chamber from escaping to by 0.25 inch (0.635cm) Zuo You of conductor pin and sealing element Outside is gone.Hole, the hole of the lower assignment of traffic of 0.25 inch of pipe screw thread, in the bottom of frame are provided with above the frame of electrode Liquid is allowed to flow into or out in frame structure with plastic fittings is provided with outside top, and on 45 degree of bevel edges of border district Be provided through 12 0.125 inch (0.3175cm) hole and lower flow distributing hole, on the surface of plate electrode and logical The thickness for crossing the high surface area of electrode chamber provides impartial flow distribution.
For anode chamber's frame, having with a thickness of 0.060 inch (0.1524cm), width is 2.875 inches (7.3025cm) and length are 5.875 inches (14.9225cm) and diameter is that 0.25 inch (0.635cm) is welded on containing there are two Two holes installation that the anode of the titanium conductor pin at its back side passes through the concave region of electrode chamber.In the positioning of the anode of depth of groove Depth is adjusted by the subsequent plastic spacer of anode, is carried out towards the edge of frame battery anode with medical grade epoxy Sealing.Anode electrocatalyst coating is Mercury (Water Star) WS-32, is suitable for oxygen being precipitated in acid and at 0.060 inch Oxidation iridium coating layer on the titanium-base of (0.1524cm) thickness.In addition, anode chamber further includes the use between anode and diaphragm The anode of anode folding screen (folding is three times), this anode are 0.010 inch (0.0254cm) thick from North America Di Nuola (EC626) titanium metal material, based on oxygen coating, for providing zero clearance anode construction (and film be in contact anode) and providing Relative to the yttrium oxide with the cathode side also pressure of the associated film from anode.
For cathode chamber frame, 316L stainless steel cathode with a thickness of 0.080 inch (0.2032cm), width 2.875 Inch (7.3025cm), length is 5.875 inches (14.9225cm) and diameter is 0.25 inch (0.635cm) containing there are two The cathode of titanium conductor pin be mounted by two holes of the concave region of electrode chamber.In the emplacement depth of the cathode of depth of groove Be adjusted by the subsequent plastic spacer of cathode, towards the edge of frame battery cathode with medical grade asphalt mixtures modified by epoxy resin it is cured carry out it is close Envelope.
Copper bar is connected to two between anode posts and cathode column to distribute electric current to electrode backing plate.Utilize 0.25 inch (0.635 centimetre) screw bolt and nut assembles with about 60in-lbs compressing force and compresses battery.Neoprene elastomers gasket (0.0625 inch (0.159 centimetre) thick) is used as the gasket between battery frame, frame space and film.
Embodiment 1
Above-mentioned battery uses the conduction of silver by combining with a thickness of the indium foil of 0.010 inch (0.0254cm) Epoxy resin is mounted on the back side of 316L stainless steel conductive plate.It is about 1um's that the cathode of multi-level high surface area, which includes thickness, Electroless plating application indium layer, is deposited on the Electroless tin coating applied in advance, has the thickness about 25 on copper braided fiber substrate micro- The thick thickness of rice.The structure of copper fiber substrate is from online the Internet provider PestMall.com (Anteater Pest control Co., Ltd processed) obtain copper mesh grid.The size of copper fiber in mesh grid is with a thickness of 0.0025 inch (0.00635cm), width are 0.010 inch (0.0254cm).The cathode material of the high surface area prepared is folded into pad, pad With a thickness of 1.25 inches (3.175cm), be highly 6 inches (15.24cm), width be 3 inches (7.62cm), it is above-mentioned to constitute The size of cathode chamber has been more than the adjustment room that thickness (shimming) is 0.875 inch to 0.25 inch.The cathode prepared has meter Good size is about 3171cm2Surface area, to then 31 times of minus plate area of region, have 91% void volume and 12.3cm2/cm3 specific surface area.Cathode pad is compressible and cathode plate and film are linked together by spring force.Contain for two layers The plastics screen of very thin (0.002 inch) in 0.125 inch of big big hole be installed in cathode screen and324 Between film.Neoprene gasket (0.0625 inch (0.159cm) thick) is used as the gasket between battery carrier and film.Anode chamber Anode electrocatalyst coating be Mercury (Water Star) WS-32, the precipitated oxygen in acid and is suitble at iridium coating layer based on oxidation. In addition, anode chamber further includes three layers of folding screen being placed between anode and film, this is the thickness from North America (EC626) DeNora Degree is the titanium metal material of 0.010 inch (0.0254cm), based on oxygen coating, for providing zero clearance anode construction (and film phase The anode of contact) and provide relative to the yttrium oxide with the cathode side also pressure of the associated film from anode.
Battery component is to tighten and be installed to work station with stainless steel bolt, it and cathode shown in FIG. 1 are anti-with identical Structure, with centrifugal catholyte circulating pump, entrance battery pH sensor and export battery pH sensor, outlet liquid stream Temperature sensor.5 microns of stainless steel glass filters are used to will be in carbon dioxide jet spray to catholyte separator volume In solution, entered in the recycle stream for returning cathode cell entrance with providing the carbon dioxide of dissolution.
The anolyte used is the solution that 5% volume is diluted by sulfuric acid, by the sulfuric acid and deionized water of reagent grade 98% Composition.
In this experiment operation, which containing 0.4mol potassium sulfate solution and is adding 2gm/L saleratus Catholyte in run, this catholyte carbon dioxide jet spray to final ph be 6.60.
Service condition:
The recycling operation of batch processing catholyte
Anolyte solution: 0.92M H2SO4
Catholyte solution: 0.4M K2SO4, 0.14mM KHCO3
Cathode flow quantity: 2.5LPM
Catholyte flow velocity: 0.08ft/sec
The battery current of application: 6amps (6000 milliamperes)
Catholyte pH range: 5.5-6.6, by periodically to catholyte solution loop back middle addition saleratus come Control.The pH value of catholyte declines with the time, and the pH value is controlled by the saleratus added.
Conclusion:
Battery voltage range: 3.39-3.55 volt (slightly below voltage when, catholyte pH value decline)
Runing time: 6 hours
Formic acid faraday's yield: it is stably held in 32%-35%, periodically calculates sampling.With reference to Fig. 7.
Last formic acid concn: 9845ppm
Embodiment 2
Using the cathode as in embodiment 1, this cathode is only clear with water in an electrochemical cell after the completion of operation It washes.
In this test run, the system is in 0.375mol potassium sulfate solution and 40gm/L saleratus is added It is run in catholyte, this catholyte is 7.05 using carbon dioxide jet spray to final ph.
Service condition:
The recycling operation of batch processing catholyte
Anolyte solution: 0.92M H2SO4
Catholyte solution: 0.4M K2SO4, 0.4M KHCO3
Cathode flow quantity: 2.5LPM
Catholyte flow velocity: 0.08ft/sec
The battery current of application: 6amps (6000 milliamperes)
Catholyte pH range: 6.75 are dropped to from 7.5 with linearly in the reaction.
Conclusion:
Battery voltage range: 3.40-3.45 volt
Runing time: 5.5 hours
Formic acid faraday's yield: being stably held in 52% and falls over time slowly under catholyte pH value Drop to 44%.With reference to Fig. 8.
Last formic acid concn: 13078ppm
Embodiment 3
Using the cathode with embodiment 1 as in embodiment 2, this cathode is only in electrochemical cell after the completion of operation In wash with water.
In this test run, the system is in 0.200mol potassium sulfate solution and 40gm/L saleratus is added It is run in catholyte, final pH value of this catholyte under carbon dioxide jet spray effect is 7.10.
Service condition:
The recycling operation of batch processing catholyte
Anolyte solution: 0.92M H2SO4
Catholyte solution: 0.2M K2SO4, 0.4M KHCO3
Cathode flow quantity: 2.5LPM
Catholyte flow velocity: 0.08 feet per second
The battery current of application: 9amps (9000 milliamperes)
Catholyte pH range: dropping to 6.65 from 7.5 with linearly in the reaction, then timing node 210, Solid carbon potassium hydrogen phthalate is added into cathode recycle loop with 10gm increment at 252 and 290 minutes, in this way in the final stage of reaction Become pH value again 7 or so again.
Conclusion:
Battery voltage range: 3.98-3.80 volt
Runing time: 6.2 hours
Formic acid faraday's yield: dropping to 60% from 75% in pH value 6.65, then with timing node 210,252 and The yield being added into cathode recycle loop at 290 minutes with 10gm increment under conditions of solid carbon potassium hydrogen phthalate rises to again 75%, last because the pH value of catholyte drops to 6.90, the Faraday's yield of formic acid is again as the time is reduced to 68%.
With reference to Fig. 9.
Last formic acid concn: 31809ppm
Embodiment 4
Using the cathode with embodiment 1, embodiment 2 as in embodiment 3, this cathode is only in electricity after the completion of operation It is washed with water in chemical cell.
In this test run, which is containing 1.40mol saleratus (120gm/L KHCO3) catholyte in Operation, final pH value of this catholyte composition under carbon dioxide jet spray effect is 7.8.
Service condition:
The recycling operation of batch processing catholyte
Anolyte solution: 0.92M H2SO4
Catholyte solution: 1.4M KHCO3
Cathode flow quantity: 2.6LPM
Catholyte flow velocity: 0.09ft/sec
The battery current of application: 11amps (11000 milliamperes)
Catholyte pH range: final 7.48 are dropped to from 7.8 or so with linearly in the reaction.
Conclusion:
Battery voltage range: 3.98-3.82 volt
Runing time: 6 hours
Formic acid faraday's yield: being stably held in 63% and falls over time slowly under catholyte pH value Drop to 54%-55%.With reference to Figure 10.
Last formic acid concn: 29987ppm
The embodiment 5 of prediction
This embodiment is related to carbonate/carbonic acid of the electrolyte by being supported by film nanofiltration (NF) (Figure 10) from potassium Hydrogen salt separation product potassium formate.Test includes two business NF films.Feedstock solution includes 1.2M saleratus plus 0.6M formic acid Potassium, and it is 7,9 and 11 that the pH value of feedstock solution, which will be adjusted separately in three independent operations (to each film),.
All NF tests will seep under conditions of adding 40bar (580psig) pressure and 50 DEG C outside in GE-Osmonic Separation (0.0137 square metre of effective membrane area) thoroughly.There to be the feed liquid of 3L to pass through and then penetrate into graduated cylinder in each reaction In (determine volume), and record runing time.Analysis total carbonate (HCO is used in after these penetrating fluids3 -And CO3 2-) and first Hydrochlorate.From these data, permeability (L/m2H Bar) and solute rejection (in%) can calculate it is as follows:
Wherein [S] indicates the molar concentration of solute, can be formates or carbonate.
Expected results are summarized as follows:
GE-Desal DK film
Dow-Filmtec NF270 film
Expected embodiment 6
Single penetration testing is carried out with DK film, this test use includes 1.2M KHCO3In addition the concentration of 1.2M potassium formate Formates charging.This test carries out under will being 11 in pH value, and other conditions will be as in embodiment 1.
Such discriminable rejection for giving total carbonate and formates 79.9% and 33.8% of test.Permeability will For 0.32L/m2h bar。
Embodiment 7
In addition to the tin ball (diameter 0.3-0.6mm) for using 701gm to contain electroless plating indium coating as cathode, the present embodiment Use the battery with embodiment 1, embodiment 2 as embodiment 3.Cathode chamber with a thickness of 0.875 inch.
In this test run, which is containing 1.40 moles potassium bicarbonates (120gm/L KHCO3) catholyte Middle operation, final pH value of this catholyte under carbon dioxide jet spray effect is 8.0.
This battery under no flooded conditions under the conditions of batch, first segment run 7.3 hours, then 1.40 moles Saleratus charging will be introduced into catholyte with about 1.4mL/ minutes speed, is acquired and is measured along with overflow.It collects Circulation sample will be used as the analysis of formic acid concn.
Service condition:
The recycling operation of batch processing catholyte
Anolyte solution: 0.92M H2SO4
Catholyte solution: 1.4M KHCO3
Cathode flow quantity: 3.2LPM
The battery current of application: 6amps (6000 milliamperes)
Catholyte pH range: pH value is in the reaction as delaying from 8 for linearly drops to 7.50.
Conclusion:
Battery voltage range: 3.98-3.82 volt
Runing time: batch mode: 7.3 hours
The overflow of charging and product: it runs 47 hours to the end within 7.3 hours.
Formates faradic efficiency is concentration of formate greater during this between 42% to 52% during gap is reacted Reach 10490ppm.During feeding with overflow, periodical computational efficiency changes between 32% to 49%.Average transfer efficiency 44% or so.Concentration of formate greater changes 10490 between 48000ppm during charging and overflow.Cell voltage exists 4.05V or so starts, and terminates in 3.80V.
Embodiment 8
Electrolysis is used containing 3 compartment glass batteries and total volume is about 80ml.The battery is constructed to airtight gather Tetrafluoroethene (Teflon) casing.Three compartments are separated by two glass mediums.Using 3 electrode assemblies.One compartment Working electrode and reference electrode (Accumet silver/silver chlorate) are accommodated, contains the Water-Electrolyte and catalyst among these.In Between compartment also contain the electrolyte and catalyst solution.The pH value of third compartment is about 4.5 and is blasting CO2's In the case of full of 0.5mol potassium sulfate electrolyte aqueous solution and being mounted with electrode (TELPRO (Stafford, TX).Mixed metal Oxide electrode.Working electrode room purifying carbon dioxide during experiment.The ion chromatography that these solution pass through formic acid Figure is measured and is analyzed before electrolysis and after electrolysis.This test is to use 6 channel Arbin tool MSTAT current potentials Under the conditions of carry out, about 1.5 hours are operated under -1.46V or -1.90V vs.SCE reference electrode.
Embodiment 9
In addition to using 890.5gm tin ball (3 mm dia) medium and tinfoil paper coating as cathode, the present embodiment uses and reality Apply the battery of example 1, embodiment 2 as embodiment 3.Cathode chamber with a thickness of 1.25 inches and the system is not feed Operation operation under conditions of input.Solution of the carbon dioxide with Sprayable to be saturated in catholyte separator.
Fill the detailed data of tin bed cathode:
Weight: 890.5gm tin ball
Tin ball: average-size 3mm
Total building volume: 369cm3
The tin grain surface area of calculating: 4,498cm2
The cathode specific surface area of the packed bed of calculating: 12.2cm2/cm3
The voidage of the packed bed of calculating: 34.6%
In this test run, the system is in 1.40mol saleratus (120gm/L KHCO3) catholyte in transport Row, it is about 8.0 that this catholyte, which is acted in carbon dioxide jet spray down toward final pH value,.
The battery is being run in the case where no overflow, and periodic harvest cathode circulation sample is as concentration of formate greater Analysis.
Service condition:
The recycling operation of batch processing catholyte
Anolyte solution: 0.92M H2SO4
Catholyte solution: 1.4M KHCO3
Cathode flow quantity: 3.0LPM
Catholyte flow velocity: 0.068ft/sec
The battery current of application: 6amps (6000 milliamperes)
Catholyte pH range: in the reaction at leisure as the slave pH of linearly about 7.62 increases pH value to the end 7.73。
Conclusion:
Battery voltage range: start in 3.84V, then slowly drop to 3.42V.
Runing time: batch processing mode, 19 hours
Formates faradic efficiency starts about 65%, and 36% is then dropped to after 10 hours, is dropped to after 19 hours 18.3%.Last concentration of formate greater runs last for 20,500ppm in 19 hours.With reference to Figure 11 and Figure 12.
Embodiment 10
In addition to using 805gm to apply indium tin ball (3 mm dia) medium, installing 0.010 in 316L stainless steel plate back side conductor The tinfoil paper of inch (0.0254cm) thickness and use conductive epoxy resin as cathode, the present embodiment using with embodiment 1, embodiment 2 battery as embodiment 3.Cathode chamber with a thickness of 1.25 inches, and the system be it is no charging input condition Lower operation operation.Carbon dioxide enters in the anti-solution of cathode in spraying form.The online tin ball of tin-coated copper use and Embodiment 1 arrives the identical method electroless plating indium of embodiment 4.The thickness of indium coating is about 0.5-1.0 microns.
It is coated with the detailed data of the tin ball packed bed cathode of indium layer:
Weight: 890.5gm is coated with the tin ball of indium layer
Tin ball: average 3mm size
Total building volume: 369cm3
The tin grain surface area of calculating: 4,498cm2
The cathode specific surface area of the packed bed of calculating: 12.2cm2/cm3
The voidage of the packed bed of calculating: 34.6%
In this test run, the system is in 1.40mol saleratus (120gm/L KHCO3) catholyte in transport Row, it is about 8.0 that this catholyte, which is acted in carbon dioxide jet spray down toward final ph,.
This battery is run in the case where no overflow, and periodic harvest cathode circulation sample is as concentration of formate greater Analysis.
Service condition:
Cathode recycling operation batch processing
Anolyte solution: 0.92mol H2SO4
Catholyte solution: 1.4mol KHCO3
Cathode flow quantity: 3.0LPM
Catholyte flow velocity: 0.068ft/ seconds
The battery current of application: 6 amperes (6000mA)
Catholyte pH range: in the reaction at leisure as the slave pH of linearly is the pH of 7.86 or so reductions to the end It is 5.51.
Conclusion:
Battery voltage range: start in 3.68V, then slowly drop to 3.18V.
Runing time: batch processing mode, 24 hours
Formates faradic efficiency starts about then to change between 60% to 85% 100%, finally small 24 When after be 60% or so.Last concentration of formate greater is finally 60000ppm in operation in 24 hours.It is molten in concentration formic acid and high salt The dilution error of sample can be seen from the variation of yield number in liquid.With reference to Figure 13 and Figure 14.
Embodiment 11
It has used and battery as embodiment 3 of embodiment 1, embodiment 2 and has newly prepared indium on the net in tough cathode Tin catalyst coating.The cathode of preparation has about 3171cm2Computational chart area, this is one piece and is equivalent to planar cathode plate face The area of 31 times of product, there is 91% voidage and 12.3cm2/cm3Specific surface area.
In this test run, the system is in 1.40mol saleratus (120gm/L KHCO3) catholyte in transport Row, it is 7.8 that this catholyte, which is acted in carbon dioxide jet spray down toward final ph, before it is being used.
The battery structure reacts first segment 8 hours under circular gap mode, reaches formate ions concentration about 20000ppm, then 1.40M saleratus charging will introduce catholyte with 1.2mL/ minutes speed.Along with the acquisition of overflow And measurement, overflow and catholyte circulation sample sample and is analyzed, and pass through the chromatography of ions progress formic acid measurement.
Service condition:
Cathode: the electroless plating indium on the tin on copper mesh substrate
Continuous feed 11.5 days in cathode circulation operation.
Anolyte solution: 0.92M H2SO4
Catholyte solution: 1.4M KHCO3
Cathode flow quantity: 3.2LPM
Catholyte flow velocity: 0.09ft/ seconds
The battery current of application: 6amps (6000 milliamperes)
Conclusion:
Cell voltage relationship at any time: Figure 15 illustrates that cell voltage changes over time as a result, showing in initial start It is about the stable operating voltage of 3.45V after 11.5 days later.
Runing time: 11.5 days
Formic acid concn relationship at any time: Figure 16 shows that formic acid concn changes with time relationship.
Formates faraday's yield: Figure 17 illustrates to measure formates yield from the sample being collected into, to calculate first The relationship of sour current efficiency at any time.
Last formic acid concn: about 28000pm.
The pH value of catholyte: Figure 18 illustrates catholyte pH value being reduced to from 7.8 slowly in 11.5 days 7.5 variation.Feed rate does not change in the process of running, but the increase or reduction that feed rate will be slow, with dimension Hold the pH value in the continuous catholyte of the pH range of any optimum operation.
Embodiment 12
The battery with embodiment 1, embodiment 2 as embodiment 3 has been used, and has newly prepared indium on the net in tough cathode Tin catalyst coating.The cathode of preparation has about 3171cm2Computational chart area, this is one piece and is equivalent to planar cathode plate face The area of 31 times of product, there is 91% voidage and 12.3cm2/cm3Specific surface area.
In this test run, the system is in 1.40mol saleratus (120gm/L KHCO3) catholyte in transport Row, it is 7.8 that this catholyte, which is acted in carbon dioxide jet spray down toward final ph, before it is being used.
The battery structure reacts first segment 8 hours under circular gap mode, reaches formate ions concentration about 20000ppm, then 1.40M saleratus charging will introduce catholyte with 1.2mL/ minutes speed.Along with the acquisition of overflow And measurement, overflow and catholyte circulation sample sample and is analyzed, and pass through the chromatography of ions progress formic acid measurement.
Service condition:
Cathode: the electroless plating indium on the tin on copper mesh substrate
Continuous feed 21 days in cathode circulation operation.
Anolyte solution: 0.92M H2SO4
Catholyte solution: 1.4M KHCO3
Cathode flow quantity: 3.2LPM
Catholyte flow velocity: 0.09ft/ seconds
The battery current of application: 6 amperes (6000 milliamperes)
Conclusion:
Cell voltage relationship at any time: this battery shows the operation voltage of higher about 4.40V, this voltage is than it Its battery will be high, this is because opposing cathode indium foil conductor plate has insufficient electrical contact pressure.This battery maintains The operation operation of one long period.
Runing time: 21 days
Formic acid faraday's yield: Figure 19 illustrates to measure formates yield from the sample being collected into, to calculate formic acid The relationship of salt current efficiency at any time.Formic acid Faradaic current efficiency drops to 20% range after 16 days.
Concentration of formate greater relationship at any time: Figure 20 shows that formic acid concn changes with time relationship.At the 21st day, work as electricity When pond is still operated with the operation rate of 6A, indium (III) carbonate of 0.5gm is added in catholyte.Before indium addition, yin The concentration of formate greater of pole liquid operation circuit is 11330ppm, and concentration of formate greater increases to after battery operation operation 8 hours Then 13400ppm increases to 14100ppm after 16 hours, run unit stops after operation operation in 21 days.
Catholyte pH value: Figure 21 illustrates pH value of catholyte during entire continuous operation, cathode electricity The pH value of matter is solved always in 7.6-7.7 range, among these in addition to the discrete data point near the 16th day when water pump stops.Into Material rate does not change in the process of running, but the increase that will be slow of feed rate or reduction maintain any best behaviour The pH value of the continuous catholyte of the pH range of work.
It is believed that can understand the disclosure and many adjoint advantages through the above description, and public affairs are not being departed from The theme opened or do not sacrifice made kit form under the conditions of all substantial advantages, the various changes in construction and arrangement are Obviously.Above-mentioned form is only its explanatory embodiment, and the purpose of appended claims is surrounded or comprising this A little variations.

Claims (10)

1. it is a kind of by Carbon dioxide electrochemical reduction at the method for product, comprising:
(A) acid anodolyte is introduced in the first compartment of the first electrochemical cell, the first compartment includes an anode；
(B) catholyte containing alkali metal hydrogencarbonate, institute are introduced in the second compartment of first electrochemical cell It states catholyte to be saturated with carbon dioxide, the second compartment includes high surface area cathode, and the high surface area cathode has Greater than 2cm2/cm3Specific surface area and including an indium coating and with 30% to 98% void volume, it is at least partly described to contain There is the catholyte of alkali metal hydrogencarbonate to be recovered；
(C) apply a potential between the anode and the cathode to be enough to make the carbon dioxide reduction at alkali metal formic acid Salt；
(D) alkali metal formate is introduced in the ion-exchange chamber of one second electrochemical cell；
(E) apply a potential between the anode of second electrochemical cell and the cathode of second electrochemical cell to be enough Generate at least formic acid and alkali metal hydroxide；And
(F) alkali metal hydroxide and alkali metal hydroxide for introducing step (E) are augmented and carbon dioxide is to generate quilt It is introduced at least part of the alkali metal hydrogencarbonate in the second compartment of first electrochemical cell.
2. according to the method described in claim 1, further comprising:
From the alkali metal hydrogencarbonate separation of the catholyte of the first electrochemical cell with a nanofiltration system The alkali metal formate.
3. according to the method described in claim 2, wherein, from the cathode of the first electrochemical cell with a nanofiltration system The alkali metal hydrogencarbonate of electrolyte separates the alkali metal formate
The alkali metal hydrogencarbonate of the catholyte is introduced into alkali metal hydroxide to convert at least partly institute Stating alkali metal hydrogencarbonate is alkali carbonate；And
The alkali carbonate is separated from the alkali metal formate with a nano-filtration unit.
4. according to the method described in claim 3, further comprising:
It introduces the alkali carbonate containing alkali metal hydroxide and carbon dioxide and is at least partly introduced into described the to generate The alkali metal hydrogencarbonate of the second compartment of one electrochemical cell.
5. according to the method described in claim 1, wherein, the acidity anodolyte includes sulfuric acid.
6. according to the method described in claim 1, further comprising:
The halogen for being selected from consisting of group: F is generated in the first compartment of first electrochemical cell2、Cl2、Br2With I2。
7. according to the method described in claim 6, wherein the method further includes:
Make the halogen and an organic compound reaction to generate a halogenated products.
8. according to the method described in claim 1, wherein homogeneity heterocyclic catalyst is used for the cathode.
9. according to the method described in claim 1, it further comprises running the first electrochemistry under superatmospheric pressure Battery.
10. the electro-catalytic coating includes according to the method described in claim 1, wherein the anode contains electro-catalytic coating Ruthenium-oxide, yttrium oxide, platinum, platinum oxide, gold or gold oxide.
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