CN101657568B - Continuous co-current electrochemical reduction of carbon dioxide - Google Patents

Continuous co-current electrochemical reduction of carbon dioxide Download PDF

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CN101657568B
CN101657568B CN2006800378108A CN200680037810A CN101657568B CN 101657568 B CN101657568 B CN 101657568B CN 2006800378108 A CN2006800378108 A CN 2006800378108A CN 200680037810 A CN200680037810 A CN 200680037810A CN 101657568 B CN101657568 B CN 101657568B
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gas
cathode
catholyte
anolyte
reactor
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CN101657568A (en
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科林·奥罗曼
李辉
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MANTRA ENERGY ALTERNATIVES Ltd (CA)
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Abstract

n various embodiments, the invention provides electro-chemical processes for reduction of carbon dioxide, for example converting carbon dioxide to formate salts or formic acid. In selected embodiments, operation of a continuous reactor with a three dimensional cathode and a two-phase (gas/liquid) catholyte flow provides advantageous conditions for electro-reduction of carbon dioxide. In these embodiments, the continuous two-phase flow of catholyte solvent and carbon dioxide containing gas, in selected gas/liquid phase volume flow ratios, provides dynamic conditions that favour the electro-reduction of COs at relatively high effective superficial current densities and gas space velocities, with relatively low reactor (cell) voltages (<10 Volts). In some embodiments, relatively high internal gas hold-up in the cathode chamber (evident in an internal gas to liquid phase volume ratio >0.1) may provide greater than equilibrium CO2 concentrations in the liquid phase, also facilitating relatively high effective superficial current densities. In some embodiments, these characteristics may for example be achieved at catholyte pH>7 and relatively low CO2 partial pressures (<10 bar). In some embodiments, these characteristics may for example be achieved under near adiabatic conditions, with catholyte outlet temperature up to about 80 DEG C.

Description

The lasting co-current electrochemical reduction of carbonic acid gas
Technical field
The present invention relates to electrochemical field, more particularly, relate to carbonic acid gas electroreduction in aqueous systems process with and equipment.
Background technology
Formate MHCO 2(wherein, M is generally Na, K or NH 4) and formic acid HCO 2H is can be by the commercial chemical goods of industrial thermochemistry synthetic (Kirk-Ohmer-Encyklopedia of Chemical TechmIogy, 1991) production.For example, can be by sodium hydroxide and reaction of carbon monoxide be obtained sodium formiate and adopt subsequently sulfuric acid solution acquisition formic acid.
NaOH+CO→NaHCO 2
2NaHCO 2+H 2SO 4→2HCO 2H+Na 2SO 4
The by product that formic acid also can be used as oxidizing hydrocarbon produces, and can produce by the methyl formate hydrolysis from carbonylation of methanol.Adopt the synthetic formate (KHCO for instance, of method of carbonic acid gas electroreduction 2) be familiar with (Chaplin and Wragg, 2003 by people; Sanchez etc., 2001; Akahori etc., 2004; Hui and Oloman, 2005).
Carbonic acid gas is considered to the main artificial origin of climate change.Therefore need to and/or convert it into useful product with carbon dioxide sequestration.
Oloman and Watkinson disclose a kind of for the trickle bed reactor with oxygen electrolytic reduction alkalize superoxide at United States Patent (USP) 3,969 in 201 and 4,118,305 (being incorporated herein the application as a reference).In all respects of this invention, electrochemical cell comprises a pair of isolated electrode, and wherein at least one electrode is the conducting block of liquid permeable, and separates by leg and another electrode.This electrode block can be the form of particle bed or the form of fixing porous matrix.This electrode block is comprised of conducting material, and its surface is the good catalyzer of the reaction that will carry out.This electrode block has the import for infusion fluid electrolytic solution and gas, and electrolytic solution and gas can for example be approximately perpendicular on the direction of the interelectrode sense of current and flow by this electrode block like this.This electrode block also has outlet, is used for comprising that the solution of reaction product discharges from the conductive block of this liquid permeable.
Summary of the invention
In various embodiments, the invention provides the electrochemical process for treating for carbon dioxide reduction, for example, convert carbonic acid gas to formate or formic acid.In the embodiment that selects, the electroreduction as carbonic acid gas that uses with flow reactor of three-dimensional negative electrode and two-phase (gas phase and liquid phase) catholyte stream provides favourable condition.In these embodiments, the continuous two phase flow of catholyte and carbon dioxide (having specific gas/liquid phase volume ratio) provides suitable CO 2The dynamic condition of electroreduction under relatively efficient surface current density.In certain embodiments, relatively high internal gas rejection (gashold-up) in cathode compartment (be the gas-liquid volume ratio＞1 in feedstream, or in porous electrode＞0.1) can provide higher than CO in liquid phase 2The CO of equilibrium concentration 2, be beneficial to surface current density relatively efficiently.For example, in certain embodiments, these features can be in catholyte pH＞7 and relatively low CO 2Dividing potential drop (＜10 bar) is lower to be obtained.
On the other hand, the present invention relates to the catholyte liquid mixture is constantly flow through the cathode compartment of electrochemical reactor.This catholyte liquid mixture can comprise carbon dioxide and be dissolved with the liquid cathode electrolytic solution of carbonic acid gas.For example, this catholyte can be the aqueous solution that is dissolved with basic metal or bicarbonate of ammonia, and it can remain on the pH of expectation, and for example its pH scope can be 6 to 9.This catholyte can keep its gas-liquid (G/L) volume ratio, the i.e. volume ratio of carbon dioxide and liquid cathode electrolytic solution.This G/L ratio can be maintained in cathode compartment, for example, is maintained in the feedstream in this cathode compartment or porous cathode.For example, can carry out this treatment process and make G/L than greater than threshold value, for example in feedstream greater than 1, or in porous (3D) negative electrode greater than 0.1.
One aspect of the present invention relates to and transmits electric current between negative electrode in cathode compartment and anode to reduce the carbonic acid gas of dissolving, to obtain the product of expectation.In certain embodiments, can carry out the method and make effective surface current density on negative electrode greater than threshold value, for example 1kA/m 2(or 1.5,2,2.5,3,3.5,4,4.5 or 5kA/m 2).For example, the electric current in system can be the direct current that is driven by electrochemical cell voltage, and in certain embodiments, the method can operate under relatively low electrochemical cell voltage, for example less than 10V.
In certain embodiments, all respects of the present invention can cooperatively interact to promote the use of processing parameter, and these processing parameters can improve the economic benefits for the treatment of process of the present invention.In certain embodiments, method of the present invention can be used relatively light input air-flow, for example density of carbon dioxide gas can from 1% to 100% in unstripped gas, or the arbitrary numerical value in this scope (in certain embodiments, produce the partial pressure of carbon dioxide lower than threshold value in cathode compartment, this threshold value can be 3,5 or 10 bar for example).Similarly, can use relatively low system pressure, for example, the cathode pressure in cathode compartment can maintain minimum value for example 1,2,3,4 or 5 bar (1 bar=100kPa (abs)) to maximum value for example in the scope of 6,7,8,9 or 10 bar.In certain embodiments, implement method of the present invention comparatively effective at higher temperature, this can be avoided cooling, for example, in the situation that cathode temperature is higher than for example 20,25,30,35,40,45 or 50 ℃ of the threshold values of expecting.In this case, should be appreciated that, the air pressure of cathode compartment and temperature can change along with cathode height.For example, the pressure of import can greater than the pressure of outlet (for example, in certain embodiments, the scope of pressure drop be from approximately 10,20,30,40 or the minimum value of 50kPa to approximately 500,600,700,800 or the maximum value of 900kPa).Similarly, the temperature of outlet can be greater than the temperature of import, and the temperature rise from import to outlet is 1 ℃ to 100 ℃, or any number in this temperature range.Should be appreciated that gaseous constituent (CO particularly 2Concentration) and total pressure determined CO 2Dividing potential drop, namely, ppCO 2=(CO 2Share) * (total pressure).
The negative electrode that uses in the present invention has effective thickness on the electric current dimension, as porous cathode.These can be called three-dimensional (3D) electrode.Such electrode has specific thickness, as less than 6,5,4,3,2,1 or 0.5mm, these electrodes also can have specific vesicular structure or porous scope, as 5% to 95% or this scope in any number, as 30%, 40%, 50%, 60% or 70%.Negative electrode of the present invention can be made by the multiple choices electroactive material, as tin, graphite, Chinese wax, mercury, indium, zinc, cadmium or other material, as be coated with conduction or the dielectric base of selectivity electroactive material (tin-coated copper, copper amalgam, zinc-plated graphite or zinc-plated glass for instance).
Anode can be arranged in the anolyte compartment, and can use the electrochemical cell barrier film that anolyte compartment and cathode compartment are separated.Anolyte in the anolyte compartment can be the hydration anolyte, and can comprise alkali metal hydroxide, salt (comprising ammonium salt) or the acid that is dissolved in wherein, and its pH scope can from 0 to 14, or any pH value in this pH scope.
This electrochemical cell barrier film can be to permeate cationic barrier film, for example can allow specific ion to pass this barrier film with the barrier film of the stoichiometric ratio in the Balance Treatment process.
The expection product of the method comprises formate, as ammonium formiate, potassium formiate and sodium formiate, or formic acid.Can adopt several different methods should expect that product separated from catholyte.For example, the part of catholyte namely reclaims catholyte again, can be recovered to from the outlet of cathode compartment the import of cathode compartment, and the expection product can be separated from the catholyte of this recovery.Similarly, at least a portion anolyte can be recovered to anolyte compartment's import again from anolyte compartment's outlet, and can isolate the anode by product from the anolyte that reclaims.
In certain embodiments, the Joule heating of antianode electrolytic solution (Joule heating) can provide the anolyte of heat, and this hot anolyte can be used for the catholyte of heating recovery to isolate the expection product from this catholyte, for example, by evaporative fractionation crystallization or vacuum distilling.In certain embodiments, the catholyte of recovery includes formate, can with anolyte reaction, by acidolysis reaction obtain the expection product.
Description of drawings
Fig. 1 is the schema of all respects of the treatment process of the embodiment of the present invention 1, wherein, and A=reometer, P=pressure gage, T=thermometer, V=voltmeter, W=humid gas under meter, PC=pressure controller;
Fig. 2 is the schematic diagram of the electrochemical cell in the embodiment of the present invention 1, and wherein drawing reference numeral represents following device: 1 and 2: pond body, 2,7 and 9: pad; 3: anode supply side (anode feeder); 4: anode clapboard (anode spacer); 5: barrier film; 6:3D negative electrode (being coated with the tin copper mesh, tin bullet/grain and plumb/grain); 8: negative electrode supply side (cathode feeder);
Fig. 3 is the cross sectional elevation of single pond reactor (reactor A) of detailed description in embodiments of the invention 1;
Fig. 4 is the cross sectional elevation of single pond reactor (reactor B) of detailed description in embodiments of the invention 1;
Fig. 5 is with CO 2Change into the schema of all respects (comprising the recovery again of anolyte and catholyte) of the continuous treating processes of formate and formic acid;
Fig. 6 is with CO 2Gas reforming becomes NaHCO 2(sodium formiate) and NaHCO 3(sodium bicarbonate) also generates by product H 2(hydrogen) and O 2The process flow sheet of the embodiment of (oxygen) (schema " A ");
Fig. 7 is the block representation for the treatment of scheme A, and it has illustrated by stable state material balance stream table and every day the about carbon dioxide of 600 tons has been changed into the technological process of sodium formiate;
Fig. 8 shows treatment scheme B, wherein shows respective material and the energy balance stream table of the embodiment of the present invention;
Fig. 9 shows the treatment scheme C in the embodiment of the present invention.
Embodiment
The invention provides a kind of for CO 2The flow reactor of electroreduction, for example, the raw material that this flow reactor can be used for comprising carbonic acid gas and water converts formate ion (reaction 1) to and and then generates the treating processes of formate or formic acid product.
CO 2+ H 2O+2e -→ HCO 2 -+ OH -(reaction 1)
In certain embodiments, the present invention can use and Oloman and Watkinson at United States Patent (USP) 3,969, the similar electrochemical reactor of disclosed trickle bed in 201 and 4,118,305.In such embodiments, the present invention can use a kind of device that relates to the electrochemical reaction of gas reactant for realization, this device comprises the electrochemical cell with a pair of electrode that separates, wherein at least one electrode for example negative electrode be the conducting block of liquid permeable, separate by ion transmitable electric insulation layer (as barrier film or porous membrane) and another electrode.This reactor can the trickle bed mode operation, reactant gases and catholyte and stream by the 3D negative electrode.As shown in this embodiment, can adjust processing parameter of the present invention, so that reaching favourable reactant, this reactor supplies with (for example higher gas space velocity, higher gas feed flow rate and reactor volume ratio) and mass transfer characteristic.In negative electrode and flow flow and can carry out on any direction relevant to gravity, for example up or down.
In reactor of the present invention, can be provided with import, be used in the conducting block with liquid electrolyte and gas inject liquid permeable, and be provided with outlet, discharge from conducting block for the solution that will comprise reaction product.The electrolytic solution that is arranged so that of import and outlet can pass through this conducting block in the mode that also flows with gas on for example vertical with interelectrode sense of current direction.For example, this reactor also has cation membrane (as disclosed in 2005 in Hui and Oloman).In optional embodiment, can use the reactor of other type.
For obtaining expecting product and satisfy comprehensive material balance, the charging of this processing can comprise: metal hydroxides and/or metal-salt be MOH, MCl, M for example 2CO 3, M 2SO 4And M 3PO 4, wherein M is generally basic metal (Na, K etc.) or NH 4Acid is H for example 2SO 4, H 3PO 4Or HCl; Or ammonia (NH 3).
Fig. 1,5,6,7,8 and 9 schema have comprised the protection domain of embodiments of the invention at the detailed step that shows in varying degrees the various optional treatment process of the present invention.In certain embodiments, with the CO that uses in present method 2Feedstream is concentrated to the CO higher than 80%vol 2Perhaps, can use relatively light gas stream, as from fossil-fuel-fired product gas (comprise the approximately CO of 10%vol 2).CO 2The reaction composition that in feedstream, other may exist comprises: oxygen, oxysulfide, oxynitride and hydrogen sulfide.Can adopt several different methods to process these compositions, as by one or more washing steps, it being eliminated, in entering the feedstream of reactor, these compositions will not exist or concentration very low (as lower than 1%vol) like this.CO 2The total pressure of feedstream and temperature can change in a relatively wide scope, and from 100 to 100kP (absolute values), the variation range of temperature is from 250 to 500K as the variation range of pressure.Due to each CO by this electrochemical reactor 2Transformation efficiency may be less than 100%, the present invention also comprises and reclaims non-switched CO like this 2Gas and recovery catholyte.
Treatment step 1 to 5 in Fig. 5 can comprise in certain embodiments of the present invention, briefly introduces below in conjunction with accompanying drawing.
Step 1. is mixed: the catholyte of raw water (adding the reactant that some prepare) and recovery is continued to mix, then this mixture constantly is transported to the cathode compartment of reactor.
Step 2. reaction: [C] negative electrode.Constantly drive reaction 1, this reaction 1 is attended by side reaction (reaction 2), and the water power reduction is generated hydrogen.
2H 2O+2e -→ H 2+ 2OH -(reaction 2)
[A] anode.Constantly drive anodic reaction.The characteristic of this anodic reaction depends on the product that expectation obtains from this treatment process.For example, if the expection principal product is formate, and by product is oxygen, and anodic reaction will be reaction 3 so.
2OH -→ 1/2O 2+ 2H 2O+2e -(reaction 3)
If the principal product of expectation is formic acid, and by product is oxygen or chlorine, anodic reaction can be respectively reaction 4 or react 5 so.Other anodic reaction also comprises the generation of peroxide salt or peroxidation acid, as peroxidation sulfuric acid (2SO 4 -→ S 2O8 2 -+ 2e -).
2H 2O → O 2+ 2H ++ 2e -(reaction 4)
2Cl -→ Cl 2+ 2e -(reaction 5)
Electrode vessel in reactor can be separated by barrier film, and this barrier film optionally allows a certain amount of positively charged ion to transfer to negative electrode from anode, so that the processing stoichiometric ratio of balance expectation.If the primary product of expectation is formate, these positively charged ions can be alkalimetal ion (Na for instance, so +, K +Or NH 4 +), as oxyhydroxide, salt or NH 3Inject anolyte.And if the primary product of expectation is formic acid, the positively charged ion of transfer comprises proton (H +), it generates in reaction 4 and/or injects anolyte as acid.
Step 3. is separated: constantly principal product (formate or formic acid) is separated from the catholyte that reclaims with by product (hydrogen).
Step 4. is mixed: constantly anode reactant and the water with needs mixes with the anolyte of recovery.
Step 5. is separated: constantly the anode by product is separated from the anolyte that reclaims.
In each step of the present invention, carbonic acid gas and water can consume and/or generate in other reaction, for example in reactor or the reaction 6 that occurs in other position of present method, 7 and 8.
CO 2+ OH -→ HCO 3 -(reaction 6)
HCO 3 -+ H +→ H 2O+CO 2(reaction 7)
H ++ OH -→ H 2O (reaction 8)
In certain embodiments, the method is included in higher surface current density (for instance, higher than 0.5kA/m2) and the lower startup reaction of current efficiency (for example, for the formic acid product, higher than 50%).Method of the present invention also comprises raw material and the energy requirement in each step of balance, to mate required reactive chemistry metering ratio, keeps simultaneously lower energy expenditure.For example, method of the present invention is that 1.3kA/m2, response voltage are that 3V, CO2 pressure are 200kPa (absolute value), when temperature is 300K, formate are had 75% current efficiency in surface current density.For the raw material balance, extremely important to the management of water.The water that injects negative electrode and/or plate tank need to be complementary with speed, electric osmose transmission and the Evaporation of reaction.The cost of the method is mainly the energy expenditure in electrochemical reaction, heating, the cooling and process that extracts.In design by suitable reactor and the method, the rationalization of thermal load, can keep lower cost.In certain embodiments, can use non-metallic catalyst.For example, US Patent No. 5284563 and US5382332 disclose can be used for carbon dioxide reduction 1,4,8,11-four a word used for translation ring four decyl nickel (nickelalkyl cyclam) catalyzer.
In certain embodiments, can use higher gas/liquid (G/L) to inject mutually volume flow ratio (for instance, G/L flow=1 is to 1000 or 10 to 200) and gas space velocity (for instance, greater than 100h in electrochemical reactor -1).In specific reactor of the present invention, G/L is increased to 10 volumes that increase less than 10% from about 5.Usually, best G/L phase volume (being expressed as " G/L " rejection) is than depending on active cathodic electrolytic solution conductivity (usually reducing along with the increase of G/L rejection), CO 2Mass-transfer performance (usually increasing along with the increase of G/L rejection) and inherent temperature and CO 2Convert the balance between the dynamics that does not rely on pH of nonreactive hydrocarbonate/carbonate in a large amount of catholyte liquid phases.
In various embodiments, have two kinds of different gas/liquids (G/L) more important than very:
(i) at reactor Raw materialVolume G/L ratio in stream, along with volumetric flow of gas is corrected to STP, the scope of this G/L ratio is 1 to 1000,1 to 500,10 to 200 or 10 to 100, or any numerical value in these scopes.For example, air-flow can be 1000ml/ minute (STP correction), and liquid stream is 20ml/ minute, the G/L[stream that obtains]=1000/20=50.
(ii) the volume G/L ratio in porous cathode, namely, the ratio of gas interception capacity and liquid interception capacity in negative electrode, for example its scope can approximate greatly 0.1 to 10 or 0.2 to 2 or 0.2 to 4, or any number in these scopes.For example, gas rejection=0.6, liquid rejection=(1-0.6), G/L[rejection]=0.6/0.4=1.5.At this, " rejection "=in hole (in the 3D electrode) ratio that particular moment is occupied by specific phase, suppose in the steady-state operation of reactor not change.Because the residence time of gas in negative electrode is shorter than the residence time of (namely, gas stream is crossed liquid) in liquid, thereby G/L[stream] be not equal to the G/L[rejection].(i) and feedstream (ii) and trapped inside value be correlated with because value (ii) depends on value and the cathode characteristic of (i), as its porousness (or voidage), shape factor and particle size.Similarly, the value of (i) value impact (ii), and with negative electrode in CO 2The gas space velocity of mass-transfer performance and reactor is relevant.
Can regulate so that (at this, the CD=current density) above-mentioned condition:
At CO 2During air pressure＜3 bar, effective CD＞1.5kA/m 2
Effective CD=[surface C D] * [current efficiency of expection product (as formate)]
At single through out-of-date, formic acid production concentration＞0.5M.
3kA/m 2Under total reactor voltage＜5 volts
Surface current density is the electric current by electrochemical cell, and this electrochemical cell is separated by the convex surfaces of respective element (as negative electrode)." convex surfaces " of parts (as negative electrode) is the surf zone of the lug boss of this element on the plane parallel with this element.For flat-panel component, this convex surfaces is equivalent in this unit of towards the zone of a side of other conducting element, for example the protrusion of cathode plane anode surface.For the element of plane grid shape, this protrusion surface is the projecting inward zone to continuous level of outline of this mesh element.
" current efficiency " is (CE) ratio between the speed of real reaction speed and acquisition when the electric currents by this electrochemical cell are all consumed by correlated response (as the reduction of carbonic acid gas) when all, generally represents with per-cent.
In certain embodiments, the present invention can move under adiabatic condition or move near under adiabatic condition.(up to 90 ℃).In certain embodiments, the CO in catholyte 2Solubleness when reducing, the increase of the temperature in fact internal motivation character to carbonic acid gas electroreduction (ERC) is more favourable.And, promote CO by control 2The factor of mass transfer in flow reactor can obtain CE preferably at higher temperature.In certain embodiments, the ability of moving under high-temperature is very important, because near the flow reactor under adiabatic condition, the Joule heating effect under high CD can raise temperature of reaction approximately 80 ℃ automatically.
Embodiment 1
Fig. 1 shows the method flow diagram of the embodiment of the electroreduction that reflects carbonic acid gas.Pure CO 2Or CO 2With N 2(gas) mixture and catholyte (liquid) are in T meet (mixing tank) combination, and then gas and liquid continue to move ahead with piston flow from here, enter cathode compartment from the bottom.Like this, electrochemical reactor can flow to line operate to heterogeneous (G/L) that also flows at cathode side.Anolyte (the KOH aqueous solution) also can upwards flow through the anolyte compartment, and is recovered in the anolyte holding tank.All gas and liquid pass through respectively each rotameter.Use pump control controlling flow, control gas stream by manual valve, to guarantee obtaining suitable gas and liquid load amount in reactor.The sight gauge that employing is arranged on the several positions shown in schema is measured import and top hole pressure and the temperature of reactor.In the reaction process that the temperature of anticathode product is controlled, antianode electrolytic solution and catholyte are all carried out precooling or preheating so that its temperature is remained on the expection level.Liquid product takes out and analyzes its concentration of formate greater from sampling point.Gaseous product from gas/liquid separation (bed of packings of graphite felt) is controlled by three-way valve, is transported to respectively Ao Ersa (Orsat) gas-analysis apparatus to carry out CO 2Analyze with CO, or be transported to the humid gas under meter measuring flow velocity, or be transported to Tai Dela (Tedlar) sampler bag to adopt gas-chromatography to carry out subsequently hydrocarbon analysis.
The DC power supply that employing is connected between anode and negative electrode carries out CO 2The electrolysis of transverse electric stream.Adopt the voltmeter that is connected with this unit to measure reactor voltage.All voltages comprise anode voltage, cathode voltage and IR pressure drop.Single electrode voltage is not measured.
Use the automatic pressure control valve with the pressure in balance anolyte compartment and cathode compartment on the anolyte production line.For prevent when cathode pressure during greater than anode pressure catholyte get around this 3D negative electrode and/or barrier film pops, such pressure equilibrium is necessary.
Many mobile strokes are under atmospheric pressure to be guided by cathode outlet.For some the mobile strokes in reactor B, manual back pressure control valve and pressure gage are set on the catholyte production line keep super-atmospheric pressure (superatmospheric pressure) in catholyte outlet.
At first method of the present invention can be carried out in reactor A (little reactor), then carries out in 7 times of large reactor B (large reactor), with the effect that proves that it improves in proportion.Two reactors all have the structure shown in Fig. 2.Reactor comprises negative electrode feed plate and 3-D negative electrode, Nafion cationic exchange membrane, anode clapboard/barrier film pillar, anode feed plate and pad.Adopt silicone glue negative electrode mesh, anode network interface card and anode clapboard to be welded on the edge of anode and negative electrode, then this electrochemical cell system is placed between two insulation mild steel plates, and adopt the SS bolt that it is compressed into one, like this to give and balanced runny nose layout.
Fig. 3 shows the cross sectional elevation of single electrochemical cell reactor A." flowing through " negative electrode of reactor has the size of the wide and 150mm high (geometric jacquard patterning unit surface) of 30mm.The thickness of negative electrode depends on the 3-D cathode material of its use.For being coated with the tin copper net electrode, single or multiple mesh layers are placed between barrier film and negative electrode feeder, so the thickness of negative electrode is the thickness of all these mesh layers, and its thickness range is 0.38 to 1.83mm; For graphite felt and clipped wire or metal elastic, this negative electrode material can be embedded between neoprene gasket two-layer, this neoprene gasket contiguous negative electrode back that contacts with the negative electrode feeder, and therefore, the thickness of negative electrode is exactly the thickness of pad, namely 3.2mm.How much (a.k.a. surface) cathodic areas perpendicular to electric current are that 30mm takes advantage of 150mm-4.5 * 10 -3m 2In reactor A, the scope of impressed current (applied) is from 1 to 14A, and has from 0.22 to 3.11kAm -2Corresponding surface current density.
In reactor B, use to be coated with tin copper mesh hole negative electrode or tin particles negative electrode.Fig. 4 show reactor B one dimension front view with tin particles fixed bed cathode with and corresponding size.In order to minimize catholyte the detouring of cathodic bed edge, specially adopt 5 trilaterals on each limit to make pads, make electrolyte stream directly flow to the center of negative electrode.Deduct the zone that trilateral occupies, the surface-area of negative electrode is 3.22 * 10 -2m 2, it is approximately reactor A (4.5 * 10 -3m 2) 7 times.In reactor B, the scope of impressed current is from 20 to 101A, and its corresponding surface current density is 0.62 to 3.20kA m -2
Reactor B is assembled according to following steps by the tin particles fixed bed cathode: (1) will mix husky sheet tin (stanniferous 99.99wt%, 3mm is thick) negative electrode feeder and be placed on neoprene gasket; (2) will be evenly dispersed on Durabla (Du Labaer) pad (3.2mm is thick) on sheet tin through pretreated tin particles, and multilayer Nat dragon mesh screen (Netlon screen) is inserted into import and the exit region of anolyte stream, with dispersion liquid and support barrier film; (3) the Nafion117 film that will wet is placed on the napex of tin particles bed, then PVC screen plate, anode SS net and anode feed device (SS plate) is stacked in order; (4) last, put into the electrochemical cell body, and adopt the bolt of 24 3/8 inches that the electrochemical cell of multilayer evenly is compressed into one.
In optional embodiment of the present invention, can use multiple cathode material.Electrochemical reduction almost can be in the periodic table of elements occurs on the metal of all families in carbonic acid gas, and generates and have optionally product of different levels.Following cathode material is more suitable for specific embodiment: deposit the graphite felt of the copper of nanostructure, the graphite felt that deposits the tin cadmium alloy, the tin net that deposits the tin of nanostructure, the plastic net that is coated with tin, copper mesh, the graphite felt that deposits tin, the copper mesh that is coated with tin, stereotype, plumb, plumbous particle, lead grid lattice and Pb-C net, tin bullet and tin particles.In last five kinds of alternative embodiments that can be used for the present embodiment in previous materials.In certain embodiments, the fine or nanostructure deposition that has height (specific) surface-area in the 3D substrate is more preferably.Other possible negative electrode can be the copper mesh that deposits nanostructure copper, the tin net that deposits nanostructure tin or the plastic net that is coated with tin, or selects Pb (lead), In (indium) or Hg (mercury) as electroactive surface.
Reactor A adopts granulated tin negative electrode (stanniferous 99.9wt%) and 100%CO 2Unstripped gas, the zinc-plated copper mesh negative electrode of its Performance Ratio that shows is slightly good.Seven times of large reactor B are used 100%CO 2Unstripped gas, the catholyte aqueous solution and the anode electrolysis aqueous solution are respectively [0.5M KHCO 3+ 2M KCl] and 2M KOH, intake pressure is 350 to 600kPa (absolute value), temperature out is 295 to 325K.In the reactor voltage range identical with reactor A (2.7 to 4.3V), for 0.6 to 3.1kAm 2Surface current density, the corresponding formate current efficiency that reactor B obtains is 91% to 63%.Obtain the formate up to 1M in the catholyte product that single passes through in reactor B.
Embodiment 2 (recovery of cathodic activity)
In embodiment 1, disclosed electrochemical reactor is pressed following structure and operation:
● anode feed device=316 stainless steel plates
● anode=304 stainless steel 10 hole patterns (10 hole/inch)
● anode clapboard=PVC " fly screen (flyproof screen) " 10 hole patterns
● separator=Nafion 117 cation membranes
● the 50 hole pattern tin particles of negative electrode=approximately, high 150mm, wide 32mm, thick 3mm
● cathodic surface area=45E-4m 2
● the tinfoil paper that negative electrode feeder=copper coin supports
Operational conditions:
● electric current=6A (namely, 1.3kA/m 2),
● catholyte=0.45M KHCO 3+ 2M KCl, anolyte=1M KOH, anode electrolysis flow quantity=40ml/min
● CO 2Gas flow=364ml (STP)/minute, catholyte flow quantity=20ml/ minute
● temperature=300K, air pressure=140-170kPa (absolute value)
Adopt the negative electrode of new tin particles, formate current efficiency (CE) is from approximately 60% dropping to 50% when being 250 minutes working time when be 30 minutes working time.The recovery of current efficiency is achieved by means of the following methods:
(i) chemical treatment of negative electrode and recycling: under room temperature, the cathode particles of using was processed 2 minutes in 11wt% nitric acid, washed in deionized water and recycle in reactor.Table 1 shows treated recovery cathodic activity in the working time of 30 minutes.
Table 1.
Recycle number of times Formate CE% in the time of 30 minutes Reactor voltage V Negative electrode feed pressure kPa (absolute value)
0 (new particle) 63 3.73 156
1 61 3.56 156
2 64 3.36 161
3 66 3.30 166
Tin particles by using hydrochloric acid and/or potassium hydroxide treatment to use can obtain identical negative electrode restoration result.
(ii) reversal of poles: under condition same as described above, adopt new tin particles, when formate current efficiency is 30 minutes from working time approximately 65% drop to working time be 360 minutes 48%.Under the electric current of 1A to reactor reversal of poles 5 minutes.The formate electric current rises subsequently and go back up to 65% when is 400 minutes working time.
Embodiment 3[increases in proportion]
In embodiment 1, disclosed electrochemical reactor is pressed following structure and operation:
● anode feed device=316 stainless steel plates
● anode=304 stainless steel 10 hole patterns (10 hole/inch)
● anode clapboard=PVC " fly screen " 10 hole patterns
● separator=Nafion 117 cation membranes
● the 50 hole pattern tin particles of negative electrode=approximately, high 680mm, wide 50mm, thick 3mm
● cathodic surface area=340E-4m 2
● the sheet tin that negative electrode feeder=2mm is thick
Operational conditions:
● catholyte=0.45M KHCO 3+ 2M KCI, anolyte=1M KOH, anode electrolysis flow quantity=60ml/ minute
● CO 2Gas flow=1600-2200ml (STP)/minute, catholyte flow quantity=20ml/ minute
● advance-go out temperature=300-314K, advance-go out air pressure=600-100kPa (absolute value).
Table 2 shows the performance of this reactor.
Table 2. reactor performance
Electric current A 20 40 94 100
Surface current density kA/m 2 0.6 1.2 2.9 3.1
Working time minute 60 80 100 17
Formate CE% 91 86 64 63
Formate production concentration M 0.28 0.54 0.94 1.03
Reactor voltage V 2.7 3.4 4.1 3.9
The acid anolyte of embodiment 4[]
Reactor is according to building in embodiment 1, and the operational conditions operation of pressing embodiment 2, but anolyte is substituted by following sodium bisulfate solution:
Operational conditions:
● catholyte=0.45M KHCO 3+ 2M KCI
● anolyte=0.5～2M Na 2SO 4+ 0.5～4M H 2SO 4
Anode electrolysis flow quantity=40ml/ minute
● CO 2Gas flow=500ml (STP)/minute, catholyte flow quantity=20ml/ minute
● temperature=300K, air pressure=140-170kPa (absolute value)
This reactor is at 1～14A (0.2～3.1kA/m 2) range of current in operation, and have corresponding 80～30% formate CE and the reactor voltage of 3.5～8V.
Its result demonstration, the method can be carried out in acid electrolyte.Different Na in anolyte +/ H +The different formate current efficiency than providing, this explanation can improve formate CE by the composition of controlling anolyte.
Embodiment 5[ammonium cation]
In certain embodiments, the present invention can use ammonium ion formic acid in next life ammonium.Reactor builds according to embodiment 1, and its operation is undertaken by the condition of embodiment 4, but adopts ammonium ion to replace the catholyte potassium ion, and anolyte is alternative by the ammoniumsulphate soln of following acidity:
Operational conditions:
● electric current=4A (namely, 0.89kA/m 2)
● catholyte=0.45M NH 4HCO 3+ 2M NH 4Cl
● anolyte=0.93M (NH 4) 2SO 4+ 0.754M H 2SO 4
Anode electrolysis flow quantity=40ml/ minute
● CO 2Gas flow=500ml (STP)/minute, catholyte flow quantity=20ml/ minute
● temperature=300K, air pressure=140-170kPa (absolute value)
This reactor operation is after 2 hours, and formate CE variation range is from 35% to 70%, and the reactor voltage conversion range is from 4.6V to 5.2V.
Its result proves, the method can be used separately ammonium ion in catholyte.For the generation of formic acid or ammonium formiate, using the ability of ammonium ion shown in schema B and C.
Embodiment 6[lead electrode]
In embodiment 1, disclosed electrochemical reactor is pressed following structure and operation:
● anode feed device=316 stainless steel plates
● anode=304 stainless steel 10 hole patterns (10 hole/inch)
● anode clapboard=PVC " fly screen " 10 hole patterns
● separator=Nafion 117 cation membranes
● negative electrode=diameter is the plumb of 0.5mm, high 150mm, wide 32mm, thick 3mm
● cathodic surface area=45E-4m 2
● negative electrode feeder=stereotype
Operational conditions:
● electric current=6A (is 1.3kA/m 2),
● catholyte=0.45M KHCO 3+ 2M KCl, anolyte=1M KOH, anode electricity
Separated flow quantity=40ml/ minute
● CO 2Gas flow=364ml (STP)/minute, catholyte flow quantity=20ml/ minute
● temperature=300K, air pressure=140-180kPa (absolute value)
This reactor operation is surpassed 2 to 6 hours, demonstrated the stable formate current efficiency of (31 ± 1) %.
Embodiment 7[treatment scheme A]
The treatment scheme of this embodiment has been shown in Fig. 6, and it shows the electrosynthesis from carbonic acid gas, water and sodium hydroxide to sodium formiate.
Based on the concept of Fig. 5, the method (Fig. 6) is with CO 2Convert NaHCO to 2(sodium formiate) and NaHCO 3(Sodium Hydrogen Carbonate), and generate by product H 2(hydrogen) and O 2(oxygen).With newly inject with the CO that reclaims 2Be compressed to about 300kPa (absolute value) and be NaHCO with itself and catholyte of reclaiming 2And NaHCO 3The aqueous solution be transported to the negative electrode of electrochemical reactor.This cathode outlet is connected to gas/liquid separation, at this, liquid is divided into two portions, and a part is directly recycled, and another part obtains main cathode product (NaHCO by evaporation and fractionation crystallization 2And NaHCO 3).The gas of this cathode outlet is sent to gas separation system (for instance, pressure-variable adsorption), obtains H 2And with non-switched CO 2Transmission goes back to re-use.The anode side of this treatment process comprises the injection of NaOH (sodium hydroxide), its sodium ion (Na +) pass cation membrane, and oxyhydroxide converts by product oxygen to and reclaims from gas/liquid separation.Cycling stream system in the method includes essential compressor and pump and is used for temperature of reactor is controlled at heat exchanger (for example C1, C2, C3) in the scope of 300～350K.
Fig. 7 shows treatment scheme A, and below show based on 600 tons of CO 2The stable state raw material balance flow table in/sky.Formate current efficiency=77%.CO 2Conversion amount/total flux=72%.
Figure S2006800378108D00161
Embodiment 8[treatment scheme B]
Electrosynthesis from carbonic acid gas, water and sodium hydroxide to sodium formiate has been shown in Fig. 8.Shown in treatment scheme with CO 2Convert HCO to 2H (formic acid) also generates by product H 2(hydrogen) and O 2(oxygen).With newly inject with the CO that reclaims 2Be compressed to approximately 300kPa (absolute value), and be NH with it with the catholyte that reclaims 4HCO 2And NH 4HCO 3The aqueous solution add that (if necessary) supporting electrolyte is (as NH 4Cl or (NH 4) 2SO 4) be transported to together the negative electrode of electrochemical reactor (U1).The fluid of cathode outlet is sent to gas/liquid separation (U3), at this, liquid is divided into two portions, a part is directly recycled, another part sends thermochemistry acidolysis reaction device/separator (U6, U7) to, obtains formic acid and sulfuric acid (generating) and carry out partial vacuum and distill to obtain overhead product aqueous formic acid and end liquid (NH in anolyte by reacting 9 4) 2SO 4, this end liquid is recovered to anode by mixing tank U8.Gas stream is sent to separator (U4) from U3, obtains H at this 2And pass through mixing tank U2 with CO 2And the CO that pair answers device 7 to generate in the acidolysis reaction device 2Be sent to together the reactor feed device.
(NH 4) 2SO 4And H 2SO 4The aqueous solution is re-used by plate tank, the NH that provides 4 +And H +Positively charged ion is sent to negative electrode by cation membrane.At by product oxygen and the proton (H of anode by reaction 4 generations +) can obtain from gas/liquid separation (U4).Then, the restored acid anolyte can be divided into (U10) two portions, and a part is used to acidolysis reaction (U6) that H is provided 2SO 4, remaining inefficacy reactant can converge again with anolyte (U8).
2NaHCO 2+ H 2SO 4→ 2HCO 2H+Na 2SO 4(reaction 9)
The material and the energy (M﹠amp that operate in the treatment scheme B under stable state have been shown in following fluid meter; E) balance.This M﹠amp; It is 80% and the each CO by electrochemical reactor that the E balance is based on formate current efficiency 2Turnover ratio is 80% this supposition.
Main and less important clean reaction (net reaction) in treatment scheme B is respectively reaction 10 and 11.
CO 2+ H 2O → HCO 2H+1/2O 2(reaction 10)
H 2O → H 2+ 1/2O 2(reaction 11)
Can select the condition of this treatment scheme to promote main clean reaction 10.The feature of the treatment scheme of this embodiment can be done following selection, to promote reaction 10:
I. the electrode materials, current density, liquid composition, liquid load, the pressure and temperature that are fit in electrochemical reactor.
Ii. acid and the salt component in holding anode electrolytic solution, make positively charged ion (H for instance, +/ NH 4 +) cross-film transmission carries out with correct ratio, balance cathodic reaction 1 and 2 speed of reaction also are controlled at desired extent with the pH of catholyte.
Iii. the pH of a large amount of catholytes remains in 4 to 10 scope, and is better between 6 to 8.
Iv. keep anolyte composition and flow and think that acidolysis reaction provides proton, generate HCO in U6 2H also makes and can arrive aqueous formic acid by Distillation recovery in U7.
V. the acid in anolyte (H for example 2SO 4) concentration greater than 1M.
Vi. the formic acid with catholyte maintains sufficiently high concentration, makes to form and to isolate HCO in U6 2H。
Vii. formic acid (HCO in the catholyte that reclaims 2) concentration higher than 1M, 5M is better.
Vii. the speed injected water to be fit to negative electrode and plate tank, to keep water balance and concentration of electrolyte, be beneficial to electrochemistry and thermochemical treatment in U1, U6 and U7.
Ix. the flow of the anolyte that reclaims and temperature are kept enough height so that evaporate formic acid with the Joule heating of electrochemical reactor in U6.
X. the anode electrolysis liquid temp that reclaims decides the anode electrolysis flow quantity by energy balance, to be reduced in the demand for heat in this treating processes higher than 320k.
The operation of this treatment process depends on that generally above-mentioned condition i is to x.This embodiment is modeled in 105 CO 2/ day benchmark on given current efficiency be 80%, CO 2When conversion amount/throughput is 80%, provide stable material and energy balance.The below has listed corresponding to the material for the treatment of scheme B and energy balance stream table, and this form comprises the continued across page.
Figure S2006800378108D00181
9 10 11 12 13 14
0.0 11.4 0.0 11.4 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0
803 550 550 0 1101 1365
0.0 100.0 100.0 0.0 0.0 0.0
100.0 0.0 0.0 0.0 0.0 0.0
11.4 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 181.7 237.4
0.0 0.0 0.0 0.0 55.7 0.0
0.0 0.0 0.0 0.0 0.0 0.0
2.2E+04 1.5E+04 1.4E+04 5.1E+02 4.9E+04 5.6E+04
L G L G L L
100 10.0 100 100 100 100
354 319 300 300 354 319
1083 1061 1356 1322
20 175437 14 294 36 42
-3.4E+08 -1.7E+08 -2.0E+08 -4.6E+06 -5.8E+08 -6.8E+08
15 16 17 18 19 20
0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0
18415 17790 61 17729 16628 422
0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0
2981 2925.6 0.0 2925.6 2743.9 0.0
841 896.6 0.0 896.6 840.9 0.0
0.0 62.5 62.5 0.0 0.0 0.0
8.1E+05 8.0E+05 3.1E+03 7.9E+05 7.4E+05 7.6E+03
L G+L G L L L
300 200 100 100 100 100
300 354 354 354 329 300
1349 1356 1356 1000
585 1804 585 549 8
-9.7E+09 -9.4E+09 -1.5E+07 -9.4E+09 -8.8E+09 -1.2E+08
Embodiment 9[treatment scheme C]
Electrosynthesis from carbonic acid gas, ammonia and water to ammonium formiate has been shown in Fig. 9.This treatment scheme is with CO 2And NH 3Convert NH to 3HCO 2(ammonium formiate) also generates by product H 2(hydrogen) and O 2(oxygen).
With newly inject with the CO that reclaims 2Be NH with the catholyte that reclaims after compression 4HCO 2The aqueous solution (for example＞1M) and a small amount of NH 4HCO 2(Ammonium Bicarbonate, Food Grade, for example 0.1M) is transported to the negative electrode of electrochemical reactor.The cathode outlet fluid is sent to separation system, to obtain NH 4HCO 2Solution and by product H 2, and the catholyte used of recycle.
With ammonia (NH 3Gas or the aqueous solution) inject absorption loop, formation (NH combines 4) 2SO 4(ammonium sulfate).Follow (NH 4) 2SO 4And H 2SO 4The aqueous solution will be by the plate tank recycle, the NH that provides 4 +And H +Positively charged ion is sent to negative electrode via cation membrane.Anode can generate by product oxygen and proton (H by reaction 4 +), and reclaim by gas/liquid separation.NH in catholyte 4 +]/[H +] than maintaining certain numerical value, to provide these ions to catholyte with given pace, be used for the stoichiometry of balanced reaction 1 and 2, generate the pH scope at about 4 to 8 the catholyte that mainly comprises ammonium formiate.
Main and less important clean reaction in treatment scheme C is respectively reaction 12 and 13.
CO 2+ H 2O+NH 3→ NH 4HCO 2+ 1/2O 2(reaction 12)
H 2O → H 2+ 1/2O 2(reaction 13)
The various variations of this scheme for example can comprise, adopt (NH 4) 3PO 4And H 3PO 4Substitute (NH 4) 2SO 4And H 2SO 4Perhaps adopt NH 4Cl and HCl substitute (NH 4) 2SO 4And H 2SO 4In a rear example, the anode by product is by reacting 5 Cl that generate 2The anode by product also comprises by reacting 14 superoxide that generate, as ammonium persulphate (NH 4) 2S 2O 8Or persulfuric acid H 2S 2O 8
2SO 4 -→ S 2O 8 -+ 2e -(reaction 14)
Reference:
Kirk-Ottrmer-Encylclopedia of Chemical Technology.John Wiley，New York，1991.
R.Chaplin and A.Wragg.“Effects of process conditions and electrodematerial on reaction pathways for carbon dioxide electroreduction with particukirreference to formate formtion.″J.Appl.Electrochem.33：1107-1123(2003).
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Although more than described various embodiment of the present invention, those skilled in the art know, can in general knowledge basic according to this area, can carry out various changes or equivalence replacement to these features and embodiment, and not depart from the scope of the present invention.These changes comprise that carrying out to various aspects of the present invention known equivalence replaces, and obtains identical result with essentially identical method.Digital scope includes the numeral of these scopes of definition.Word used herein " comprise " be open-ended term, substantially be equivalent to phrase and " include, but are not limited to ", and word " to comprise " be also to have identical implication.Except explicitly pointing out in context, expression form used herein " " and " being somebody's turn to do " comprise a plurality of indication things, unless context explicitly points out.Therefore, for example, mention that " things " comprises more than one this things.Reference cited herein is not to think that this reference is exactly with respect to prior art of the present invention.Any existing document, the publication quoted in specification sheets include but not limited to patent and patent application, at this in conjunction with for referencial use.Present invention resides in all embodiment and the variation thereof described in detail by reference to the accompanying drawings in application documents.

Claims (14)

1. an electrochemical method that is used for reducing carbon dioxide, is characterized in that, comprising:
A) the catholyte liquid mixture is constantly flow through porous cathode in the cathode compartment of electrochemical reactor, described catholyte liquid mixture comprises cathode gas and liquid cathode electrolyte solvent, and described cathode gas comprises that carbon dioxide and described liquid cathode electrolyte solvent are dissolved with carbonic acid gas;
B) the gas-liquid volume of keeping the catholyte in cathode compartment is held back than equaling 1.5, and described gas-liquid volume is held back than being the volume of cathode gas and the ratio of the volume of liquid cathode electrolytic solution;
C) between the described porous cathode of cathode compartment and anode delivered current reducing the carbonic acid gas of dissolving, thereby obtain the expection product, described expection product is formate or formic acid.
2. method according to claim 1, is characterized in that, described cathode gas is through the scope from 1 to 1000 of STP correction and the gas/liquid volume ratio in reactor feed stream.
3. method according to claim 1 and 2, is characterized in that, cathode compartment maintains cathode pressure, and the scope of described cathode pressure is that 1 bar (100kPa (absolute value)) is to 10 bar (1000kPa (absolute value)).
4. method according to claim 1, is characterized in that, described catholyte solvent is to comprise the following wherein at least a aqueous solution:
Heavy carbonic basic metal or the formic acid basic metal of dissolving;
Heavy carbonic ammonia or the ammonium formiate of dissolving; With
Ammonium ion.
5. method according to claim 4, is characterized in that, the pH value scope of described catholyte solvent is 4 to 10.
6. method according to claim 1, is characterized in that, described anode is positioned at the anolyte compartment, and described anolyte compartment and described cathode compartment are separated by the electrochemical cell barrier film.
7. method according to claim 6, is characterized in that, described anolyte compartment comprises anolyte.
8. method according to claim 7, is characterized in that, described anolyte is the hydration anolyte.
9. method according to claim 8, is characterized in that, described anolyte comprises:
A) alkali metal hydroxide of dissolving;
B) ammonium salt;
C) acid of dissolving, be H 2SO 4, HCl or H 3PO 4; Or
D) sulfuric acid and the ammonium sulfate of dissolving.
10. method according to claim 8, is characterized in that, described anolyte comprises ammonium ion.
11. method according to claim 6 is characterized in that, described electrochemical cell barrier film allows specific ion to pass described barrier film with the stoichiometry of balanced reaction process.
12. method according to claim 1 is characterized in that, described formate is ammonium salt.
13. method according to claim 12 is characterized in that, further comprises from the cathode compartment outlet reclaiming at least a portion catholyte solvent to the cathode compartment import.
14. method according to claim 1 is characterized in that, further comprises from the anolyte solvent that reclaims isolating the anode by product.
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