WO2017034905A1 - Carbon activation method - Google Patents
Carbon activation method Download PDFInfo
- Publication number
- WO2017034905A1 WO2017034905A1 PCT/US2016/047482 US2016047482W WO2017034905A1 WO 2017034905 A1 WO2017034905 A1 WO 2017034905A1 US 2016047482 W US2016047482 W US 2016047482W WO 2017034905 A1 WO2017034905 A1 WO 2017034905A1
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- WIPO (PCT)
- Prior art keywords
- mixture
- carbon
- heating
- carbon source
- pellet
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims description 72
- 230000004913 activation Effects 0.000 title description 17
- 239000008188 pellet Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 13
- 239000004634 thermosetting polymer Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 8
- 239000011874 heated mixture Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920001568 phenolic resin Polymers 0.000 claims description 12
- 239000002010 green coke Substances 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000005187 foaming Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000011260 aqueous acid Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 20
- 238000001994 activation Methods 0.000 description 20
- 239000000654 additive Substances 0.000 description 17
- 239000003513 alkali Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 235000013312 flour Nutrition 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- -1 poly(vinyl alcohol) Polymers 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004484 Briquette Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 244000078856 Prunus padus Species 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/384—Granulation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the disclosure generally relates to the field of energy storage devices.
- Fig. 2 shows an exemplary pore size distribution of the activated carbon of the present methods.
- Fig. 4 shows a graph of filter resistance versus particle size.
- Electrode energy storage is needed in many applications, such as electric/hybrid vehicles, portable electronic devices, power systems, etc. Batteries of various kinds have been used for most applications.
- electrochemical double layer capacitors EDLCs, a.k.a. ultracapacitors or supercapacitors
- EDLCs electrochemical double layer capacitors
- Activated carbon or active carbon is the most widely used material in EDLCs because the carbon has a very large surface area, good electrical and ionic conductivity, excellent chemical stability, and low cost.
- activated carbon can be prepared by carbonizing a carbonaceous precursor in an inert atmosphere (e.g.,N 2 or Ar), at a high temperature (commonly hundreds of degrees Celsius), followed by physical (e.g., using CO2 or steam) or chemical (e.g., using KOH, K2CO3, NaOH, Na 2 C0 3 , A1C1 3 , ZnCl 2 , MgCl 2 , or H3PO4, etc.) activation.
- Precursors include natural materials (such as coal, nut shells, wood, biomass, etc.) and synthetic materials (mostly polymers such as phenolic resin, poly(vinyl alcohol) (PVA), polyacrylonitrile (PAN), etc.).
- Activated carbons derived from non-lignocellulosic sources have been described (see commonly owned and assigned US Patent Nos. : 8318356 and 8784764).
- a chemical activation process yields a carbon product having superior performance compared to a physical activation process.
- the most significant of the chemical activation processes involves alkali activation, i.e., reaction of either KOH or NaOH with the carbon because this process yields carbon with the highest electrical performance properties.
- this process poses some significant safety and equipment issues which limit the utility.
- the activation takes place in at from 700 to 900°C, and since KOH melts at about 400°C, a significant amount of potassium metal vapor is generated, which has two consequences.
- the furnace can easily corrode reducing the furnace life and may cause a safety hazards that needs to be addressed via expensive safety measures.
- a silicon carbide lined furnace may be used to reduce corrosion issue.
- the cost of the furnace is then significantly higher.
- the reaction of alkali and carbon typically generates foam during activation due to the release of several gasses.
- the gases released can include, for example, CO, CO2, H 2 0, and H 2 . These gases can cause severe foaming of the batch mixture.
- the extent of foaming limits the use of the space in the reactor vessel, such as to from about 10 to 30 vol%. So that only a minor amount of the reactor vessel, e.g., about 20 vol%, can be filled with the feed reactants, which can severely limit the output of the batch reactor and can increase processing costs and product costs.
- Another known preparative activation method involves: mixing an inert (i.e. non-reactive) hydrophilic polymer (e.g., polyether); forming a pellet of the carbon, the KOH, and the polymer; and heating the pellet in an inert environment to activate the carbon.
- the method reduces K volatilization due to reduced geometric surface area of the pellet or briquette compared to free powder, which briquetting reduces the corrosion issue by internal containment, and leads to lower costs.
- the method is applicable only to a very fine particle sizes, for example,, 5 microns or less, and does not work with large particle size carbon (e.g., 100 micron) needed for an industrially viable process.
- the disclosure provides a method of making activated carbon comprising: compressing a mixture comprising an alkali metal hydroxide, a carbon source, and a solid thermosetting polymer precursor into a pellet; and
- a first heating of the compressed mixture at from 600 to 1 ,000 °C, for from 10 minutes to 24 hours, for example, 850°C for 2 hrs.
- thermosetting polymer precursor refers to the phase state of the precursor at ambient temperatures.
- the method can further comprise crushing the resulting compressed and heated activated carbon product prior to the washing.
- the first heating can be accomplished, for example, in a container that is open to an external atmosphere, such as a crucible in a furnace having ambient air or an inert atmosphere.
- the alkali metal hydroxide can be, for example, powdered KOH, powdered NaOH, and like powdered alkali metal hydroxides
- the carbon source can be, for example, powdered green coke
- the thermosetting polymer precursor can be, for example, a mixture of a phenolic resin and a cross-linking agent.
- the alkali metal hydroxide and the carbon source can be, for example, in a weight ratio of from 1 : 1 to 4: 1 , such as 2: 1 , including intermediate values and ranges.
- the second heating can be accomplished, for example, in a forming gas, in an inert gas, or in a combination thereof.
- the washing can be accomplished, for example, successively with water and then a dilute aqueous acid, or concurrently with a mixture of water and a dilute aqueous acid.
- the disclosure provides a method of making activated carbon, which method provides improved efficiency and cost benefits.
- the disclosure provides a method where the solid additive is used as a binder for pelletizing a mixture of the carbon source and the alkali reactant (e.g., KOH).
- the alkali reactant e.g., KOH
- a crosslinking reaction of the reactive oligomer i.e., the phenolic resin
- the crosslinking of the reactive oligomer is followed by the activation reaction in a second heating at, for example, 600 to 1000°C.
- the crosslinked oligomer product also goes through the carbonization and activation to yield a high performance nanostructured carbon increasing the activated carbon yield, which is in contrast to an entirely sacrificial material such as an polyethylene glycol.
- the pelletization can use a carbon source having a median particle size of 100 microns, or more, to fashion pellets, which is a significantly larger particle size compared to an apparent particle size upper limit of about 5 to 10 microns in the aforementioned US 8927103.
- the solid oligomeric additive in the disclosed methods is subsequently carbonized and activated in situ to become part of the activated carbon product.
- the disclosed methods are advantaged for at least the following reasons:
- the methods can eliminate foaming by, for example, greater than 50 vol%;
- the methods provide an increased production rate
- the methods provide for efficient processing of 100 microns or larger carbon source particles that enable practical industrial scale manufacture.
- the present disclosure provides methods that use a solid reactive pre-polymer, such as a cross-linkable Novolac phenolic resin, which when added to a mixture of a suitable carbon source and alkali (such as KOH) can: eliminate foaming without introducing by-products or contaminants (e.g., fats); and permit the use of a large particle size carbon (e.g., 100 microns).
- a solid reactive pre-polymer such as a cross-linkable Novolac phenolic resin
- alkali such as KOH
- the disclosed methods use a crosslinkable solid additive in combination with a mixture of alkali and carbon.
- the solid reactive thermosetting polymer precursor additive can be, for example, a phenolic resin, such as a Novolac (e.g., available from Plenco). This resin is different from phenolic Resols, which can be a solid or aqueous solution containing about 30% water.
- phenolic Resols could also be used, the disclosed method preferably does not use a Resol resin, which has limited shelf life because the Resol resins continue to polymerize at even ambient temperatures (see www.plenco.com/phenolic-novolac-resol-resins).
- the Novolac resin binds well with the mixture of KOH powder and the carbon powder, and can form chemical bonds with itself in a curing or cross-linking reaction.
- the Novolac resin goes through a softening stage at about 65 to 105°C, followed by the crosslinking reaction, which crosslinking is complete at about 120°C. After the cure (i.e., the 120°C) the crosslinked polymer resin is strongly bonded the other ingredients.
- Another significant property of the Novolac resin additive is that on sufficiently high heating during the subsequent activation process in an inert environment, as presently disclosed, the resin maintains a robust fused pellet formed in the compression or pelletization step.
- the carbon particle size is not a significant constraint for the disclosed method since, for example, a 100 microns carbon particle size powder or larger can be easily and readily processed.
- the additional carbon content that arises from carbonization of the Novolac resin additive during the disclosed methods can also be contemporaneously activated in situ to a high performance carbon, which result increases the activated carbon net yield, and avoids additional or unnecessary steps for removal of the Novolac resin.
- Fig. 3 shows exemplary chemical structures for a phenol formaldehyde based compound such as a phenolic Novolac resin.
- washing the activated carbon product in water and acid can be a significant cost step in manufacture of activated carbon, it is desirable to have a cost effective washing.
- the larger carbon particle size range of the carbon produced in the disclosed process is advantaged by enabling significantly higher washing and filtration rates. It is known that filtration rate is an inverse function of filtration resistance, and that filtration resistance is inversely proportional to the particle size. This happens because during filtration, particles tend to form a filter cake. A high density filter cake and smaller particle sizes increase the resistance to filtration.
- a 14 mm punch was used to punch electrodes from the electrode sheet.
- the punched electrodes were dried overnight at 120°C in a vacuum oven. After transferring the electrodes to a glovebox, they were fashioned into a standard aluminum/stainless steel casing for the positive/negative electrodes in a coin cell with 90 microL of 1.2 M triethylmethyl ammonium tetrafluoroborate (TEMA-TFB) in acetonitrile(AN) electrolyte composition and a cellulose separator.
- the coin cells were tested according to standard electrochemical procedures to measure performance.
- the carbon had a measured capacitance performance of 1 l OF/cc in the EDLC button cell.
- Example 1 was repeated with the exception that Novolac resin was replaced with a polyethylene glycol (Sigma- Aldrich, Cat. No. P3015, average molecular weight 200)(see the aforementioned US 8927103 (WO2011110543A1), to original assignee SGL, now assigned to Coming, Inc.).
- a pellet was made with KOH and green coke carbon as Example 1. The particle size of the selected green coke carbon was 100 microns. The pellet was heated with the same schedule as Example 1.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201680048638.XA CN107924766A (en) | 2013-07-26 | 2016-08-18 | Carbon activation method |
KR1020187007135A KR20180042288A (en) | 2015-08-21 | 2016-08-18 | Carbon activation method |
JP2018508630A JP2018532672A (en) | 2013-07-26 | 2016-08-18 | Carbon activation method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/832,128 US20170053748A1 (en) | 2013-07-26 | 2015-08-21 | Carbon activation method and energy storage device thereof |
US14/832,128 | 2015-08-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017034905A1 true WO2017034905A1 (en) | 2017-03-02 |
Family
ID=56801847
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2016/047482 WO2017034905A1 (en) | 2013-07-26 | 2016-08-18 | Carbon activation method |
Country Status (2)
Country | Link |
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KR (1) | KR20180042288A (en) |
WO (1) | WO2017034905A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019182703A (en) * | 2018-04-10 | 2019-10-24 | リグナイト株式会社 | Composite carbon material and its production method |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050181941A1 (en) * | 2002-04-22 | 2005-08-18 | Nozomu Sugo | Method for manufacturing activated carbon, polarizable electrode, and electric double-layered capacitor |
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- 2016-08-18 WO PCT/US2016/047482 patent/WO2017034905A1/en active Application Filing
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JP2019182703A (en) * | 2018-04-10 | 2019-10-24 | リグナイト株式会社 | Composite carbon material and its production method |
JP7065508B2 (en) | 2018-04-10 | 2022-05-12 | リグナイト株式会社 | Manufacturing method of composite carbon material |
Also Published As
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KR20180042288A (en) | 2018-04-25 |
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