WO2012160229A1 - Composition de matière carbonée pouvant être obtenue par carbonisation d'un biopolymère supporté sur de l'argile - Google Patents
Composition de matière carbonée pouvant être obtenue par carbonisation d'un biopolymère supporté sur de l'argile Download PDFInfo
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- WO2012160229A1 WO2012160229A1 PCT/ES2012/070362 ES2012070362W WO2012160229A1 WO 2012160229 A1 WO2012160229 A1 WO 2012160229A1 ES 2012070362 W ES2012070362 W ES 2012070362W WO 2012160229 A1 WO2012160229 A1 WO 2012160229A1
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- Prior art keywords
- carbonaceous material
- clay
- biopolymer
- preparing
- composition according
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 229920001222 biopolymer Polymers 0.000 title claims abstract description 41
- 238000003763 carbonization Methods 0.000 title claims abstract description 9
- 239000004927 clay Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000004113 Sepiolite Substances 0.000 claims abstract description 23
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 23
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 22
- 108010010803 Gelatin Proteins 0.000 claims abstract description 21
- 239000008273 gelatin Substances 0.000 claims abstract description 21
- 229920000159 gelatin Polymers 0.000 claims abstract description 21
- 235000019322 gelatine Nutrition 0.000 claims abstract description 21
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 21
- 239000006260 foam Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 8
- 102000008186 Collagen Human genes 0.000 claims abstract description 7
- 108010035532 Collagen Proteins 0.000 claims abstract description 7
- 229920001436 collagen Polymers 0.000 claims abstract description 7
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 7
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001661 Chitosan Polymers 0.000 claims abstract description 6
- 229920002494 Zein Polymers 0.000 claims abstract description 6
- 229940072056 alginate Drugs 0.000 claims abstract description 6
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 6
- 229920000615 alginic acid Polymers 0.000 claims abstract description 6
- 235000010987 pectin Nutrition 0.000 claims abstract description 6
- 239000001814 pectin Substances 0.000 claims abstract description 6
- 229920001277 pectin Polymers 0.000 claims abstract description 6
- 229910000275 saponite Inorganic materials 0.000 claims abstract description 6
- 239000005019 zein Substances 0.000 claims abstract description 6
- 229940093612 zein Drugs 0.000 claims abstract description 6
- 229920002907 Guar gum Polymers 0.000 claims abstract description 5
- 108010055615 Zein Proteins 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 5
- 239000001913 cellulose Substances 0.000 claims abstract description 5
- 229920002678 cellulose Polymers 0.000 claims abstract description 5
- 235000010980 cellulose Nutrition 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 5
- 239000000665 guar gum Substances 0.000 claims abstract description 5
- 235000010417 guar gum Nutrition 0.000 claims abstract description 5
- 229960002154 guar gum Drugs 0.000 claims abstract description 5
- 108020004414 DNA Proteins 0.000 claims abstract description 4
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 3
- 238000011282 treatment Methods 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract 3
- 229960005188 collagen Drugs 0.000 claims abstract 3
- 229940014259 gelatin Drugs 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 38
- 239000002243 precursor Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000000265 homogenisation Methods 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000010411 electrocatalyst Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000352 supercritical drying Methods 0.000 claims description 4
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000008030 elimination Effects 0.000 claims description 3
- 238000003379 elimination reaction Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 2
- -1 stevensite Chemical compound 0.000 abstract description 2
- 229910052900 illite Inorganic materials 0.000 abstract 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000002609 medium Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 230000008901 benefit Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- NIBWUYQJNUYJNA-UHFFFAOYSA-N [C+4].[O-][Si]([O-])([O-])[O-] Chemical class [C+4].[O-][Si]([O-])([O-])[O-] NIBWUYQJNUYJNA-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940045110 chitosan Drugs 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012520 frozen sample Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229960000292 pectin Drugs 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
- C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Definitions
- the present invention relates to carbonaceous materials supported on clays provided with electrical conductivity using clays and polymers of natural origin or biopolymers as precursors.
- the present invention relates to the process of obtaining said materials by carbonization of the biopolymer previously associated with clay by heat treatments.
- the present invention also makes reference to the use of said materials as a polymer matrix charge, providing them with electrical conductivity, to their forming as conductive foams, as elements of electrical and electrochemical devices such as supercapacitors, electrocatalysts and biosensors.
- a strategy applied to the preparation of high specific surface carbonaceous materials is to associate the precursor organic material to porous solids such as silica, either synthetic (Wang, H. C, L, B. L, L, JT , Lin, P., Bian, XB, L ⁇ , J., Zhang, B. and Wan, ZX "Direct synthesis of mesoporous carbon from the carbonized of hydroxypropyl- [beta] - cyclodextrin / silica composite and its catalytic performance. "Applied Surface Science 257, 4325) or of biogenic origin (Liu, D., Yuan, P., Tan, D., Liu, H., Fan, M., Yuan, A ., Zhu, J.
- clays as a support material for carbonaceous compounds has been developed mainly with laminar-type clays such as Montmorillonite (Santos, C, Andrade, M., Vieira, A. L, Martins, A., Pires, J., Freiré, C. and Carvalho, AP (2010) "Templated synthesis of carbon matenals mediated by porous clay heterostructures.” Carbon 48, 4049; Montilla, F., Morallón, E., Vázquez, J. L, Alca ⁇ iz-Monge, J., Cazorla-Amorós, D. and Linares-Solano, A. (2002).
- Montmorillonite Suddenos, C, Andrade, M., Vieira, A. L, Martins, A., Pires, J., Freiré, C. and Carvalho, AP (2010) "Templated synthesis of carbon matenals mediated by porous clay heterostructures.” Carbon 48, 4049; Montilla,
- Carbon-ceramic composites from coal tar pitch and clays application as electrocatalyst support. Carbon 40, 2193) and to a lesser extent with fibrous clays such as palygorskite (Bispo, TS, Ba n, GB, Giménez, IF and Barreto, LS (201 1) "Semiconductor carbon composite from coir dust and sepiolite.” Materials Characte zation 62, 143) and sepiolite (Fernandez-Saavedra, R ., Darder, M., Gomez-Aviles, A., Aranda, P. and Ruiz- Hitzky, E. (2008).
- fibrous clays such as palygorskite (Bispo, TS, Ba n, GB, Giménez, IF and Barreto, LS (201 1) "Semiconductor carbon composite from coir dust and sepiolite.” Materials Characte zation 62, 143) and
- biopolymers such as gelatin or collagen containing said element
- biopolymers are per se precursors of carbonaceous compounds that can provide electrical conductivity. This is the case of gelatin (Larsen, EC and Walton, JH (1940). "Activated Carbon as a Catalyst in Certain Oxidation-Reduction Reactions.” The Journal of Physical Chemistry 44, 70) that has recently been used for the preparation and application of carbonaceous materials for electrochemical devices (C ⁇ , Y., Ge, J., Wang, XF, Chen, WH, Guo, YC and Chen, LJ (2007).
- a first aspect of the present invention relates to a carbonaceous material comprising a clay and carbon generated by heat treatment of carbonization of biopolymers. Therefore, precursor materials in the present invention are understood as the clay and biopolymer assembly.
- the present invention relates firstly to a composition of carbonaceous material characterized in that it comprises carbonaceous material supported on clay and which is obtainable by a carbonization treatment of at least one biopolymer associated with at least one clay.
- clay in the present invention are those silicates of natural or synthetic origin of laminar or smectitic type such as montmorillonite, hectorite, saponite, stevensite, Hita, beidelite and combinations of the above, or microfibrous type such as sepiolite or palygorskita, also known as attapulgita, and combinations of them.
- This group also includes derivatives of clays subjected to heat treatments to dehydrate or dehydroxylate them.
- biopolymer in the present invention are those polymers of natural origin of the polysaccharide type such as chitosan, alginate, pectin, guar gum, cellulose and their derivatives; proteins such as gelatin, collagen, zein; nucleic acids such as DNA, and combinations of the above.
- the use of clays is an advantage in the present invention over the use of other inorganic solids because of its colloidal stability in aqueous medium, its high specific surface area, its reduced cost and its non-toxic or contaminating character since they are considered inert from the point of environmental view
- the clay that is selected is sepiolite, palygorskite, bentonite or montmorillonite.
- the clay that is selected is sepiolite.
- sepiolite is considered advantageous because its aspect ratio and in general its fibrous morphology is maintained in the supported carbonaceous material of the invention.
- sepiolite of rheological grade is used, that is to say with the ability to flow, with which very stable gels are obtained in polar liquid media, facilitating the preparation of dispersions of filamentous carbon materials object of the present invention.
- sepiolite of lesser degree of purity or different granulometry implies the prior preparation of a gel or dispersion by means of prior wet grinding and ultrasonic application.
- biopolymers in the present invention represent an advantage over the use of other organic precursors in their solubility, ability to form stable gels, because of their affinity towards the surface of clay-like silicates by strongly associating with them, because of their biodegradable, biocompatible nature, Non-toxic and with very little polluting power.
- biopolymer that is selected is gelatin.
- gelatin is considered advantageous because it allows a good reversible control of its gelation state by varying the temperature of the medium, which is an advantage when it comes to forming materials as foams. Other advantages are its high water solubility, its relatively low cost and its high nitrogen content of great convenience in the preparation of conductive carbonaceous materials.
- gelatin that is selected is gelatin type A, of porcine origin.
- the precursor materials are associated with each other in a liquid medium.
- the liquid medium is selected in a preferred embodiment from the list comprising water, alcohols, carbonyl compounds, combinations of carbonyl compounds or any combination of the foregoing.
- the present invention also relates to a process for obtaining supported carbonaceous materials provided with electrical conductivity using biopolymer precursors associated with clays.
- the present invention relates to the process of obtaining said materials by carbonization of the biopolymer previously associated with clay by heat treatments.
- the present invention relates to a method of obtaining the composition as described above, comprising the steps: a. adding the precursors to a polar liquid medium as described above, b. homogenization of the composition obtained in step (a) by mechanical agitation c. recovery of the solid resulting from step (b) by elimination of the liquid medium d. heat treatment of the material generated in stage (c)
- the precursor materials are initially in the clay / biopolymer mass ratio between 10: 1 and 1: 1. In another more preferred embodiment the precursor materials are initially in the 1: 1 mass ratio clay / biopolymer.
- the precursor materials are mixed with the liquid medium in a mass ratio between 1: 1000 and 1: 10. In another more preferred embodiment, the precursor materials are mixed with the liquid medium in a proportion of 5%. by mass (50 g of precursor per kg of liquid medium).
- step (b) the homogenization mentioned in step (b) is carried out in periods of 15 minutes to 3 hours. In a more preferred embodiment the homogenization is carried out in a period of 30 minutes.
- the homogenization is carried out at the most favorable temperature so that the biopolymer is in the form of the sun.
- the homogenization of the gelatin-containing precursor is carried out at a temperature of 60 ° C.
- step (c) the removal of the liquid medium mentioned in step (c) is carried out by filtration.
- the removal of the liquid medium mentioned in step (c) is carried out by centrifugation. In another more preferred embodiment, the removal of the liquid medium mentioned in step (c) is carried out by forced evaporation under reduced pressure and at a temperature above 25 ° C.
- the removal of the liquid medium mentioned in step (c) is carried out by supercritical drying. In another more preferred embodiment the removal of the liquid medium mentioned in step (c) is carried out by lyophilization in a temperature range between 77K and 273K. In another preferred embodiment the heat treatment mentioned in step (d) is carried out under a non-oxidizing atmosphere.
- the heat treatment mentioned in step (d) is carried out under a nitrogen atmosphere in flux.
- the heat treatment mentioned in step (d) the nitrogen flow is set at 5 ml / minute.
- step (d) the heat treatment mentioned in step (d) is carried out at temperatures between 550 and 1200 ° C.
- the heat treatment mentioned in step (d) is carried out at a temperature of 800 ° C.
- Another aspect of the present invention relates to a product that is a composition of carbonaceous material characterized in that it comprises a charred mixture of at least one biopolymer supported on at least one clay.
- Particular embodiments refer to the clay being selected from a laminar type clay, a fibrous clay and combinations thereof.
- the laminar clay is selected from montmorillonite, saponite, beidellite, estevensite, Hita, and combinations thereof, or the arciall is fibrous and is selected from sepiolite, palygorskite and combinations thereof.
- the biopolymer can be chitosan, alginate, pectin, guar cellulose gum, gelatin, collagen, zein, DNA and any combination thereof.
- Said product is a composite or composite material consisting of carbonaceous compounds supported on clays, which has the advantage over non-supported carbonaceous materials of having a greater specific surface and showing a controllable morphology, also presenting electrical conductivity.
- the present invention relates to the use of said materials as a polymer matrix charge to confer electrical conductivity, to its conformation as conductive foams, to its use as elements of electrical and electrochemical devices such as supercapacitors, electrocatalysts and biosensors.
- the present invention relates to the use of the product described above, as a polymer charge to provide them with electrical and thermoelectric properties, as a collector component of sensors and electrocatalysts, as a component of supercapacitors and battery electrodes, electromagnetic radiation sealant.
- the product of the invention formed as foams its use refers to the development of conductive composites by filling the porous structure of the foam with polymers of different nature.
- Figure (a) is a scanning electron microscopy (FE-SEM) image of the carbonaceous material supported on clay of the invention prepared using gelatin and sepiolite.
- Figure (b) is a scanning electron microscopy image of the carbonaceous material prepared using gelatin without the presence of a clay.
- Figure (c) is a transmission electron microscopy image of the carbonaceous material supported on clay of the invention prepared using gelatin and sepiolite where the morphology of the carbonaceous material influenced by the morphology of the clay can be observed.
- FIG. 2 Photographic image of the foams obtained from the previous lyophilization of the precursors of the carbonaceous material before (figure c) and after heat treatment (figure b).
- Figure (a) corresponds to the conductive foam shown in Figure (b) after filling and curing process with an epoxy resin.
- Example 1 Preparation of a sepiolite supported carbonaceous material from this clay and gelatin in a 1: 1 ratio
- the material obtained is dried in an oven at a temperature of 40 ° C for 12 hours and charred in a tubular oven under a flow of nitrogen of 5 ml / minute for 2 hours.
- the oven temperature increases by 5 ° C / minute to reach 800 ° C, at which temperature it is maintained for 2 hours.
- the material obtained is characterized by scanning electron microscopy with field effect (FE-SEM) and the nanoparticulate nature of the carbonaceous solid generated can be observed (Figure 1 a).
- FE-SEM scanning electron microscopy with field effect
- Figure 1b The same procedure applied to a material without the presence of sepiolite generates carbonaceous particles of mass appearance
- Example 3 Preparation of a conductive composite by filling carbonaceous foam with epoxy resin.
- a conductive foam is prepared according to the procedure described in Example 2. Subsequently, 13.7 grams of a stoichiometric mixture of epoxy resin (diglycidyl ester of bisphenol A) and a diamino compound (polypropyleneglycol (bis-2-aminoeter)) are added before Cure occurs. Dynamic vacuum is applied to the foam assembly with the formulation of the epoxy resin and the diamino compound until the pores of the carbonaceous foam are filled with polymeric material. Finally, the resin is cured at 60 ° C for 12 hours followed by a post-cure of 2 hours at 120 ° C. The final material can be easily machined to expose its conductive faces.
- epoxy resin diglycidyl ester of bisphenol A
- a diamino compound polypropyleneglycol (bis-2-aminoeter)
- the volumetric conductivity of the material measured after the deposition of a layer of gold by sputtering as a contact element is 0.01 S.cm "1.
- the macroscopic appearance of the conductive carbonaceous foam - epoxy resin composites is presented in Figure 2a .
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Abstract
La présente invention concerne une composition de matière carbonée caractérisée en ce qu'elle comprend une matière carbonée supportée sur de l'argile, ladite argile étant de préférence de type laminaire comme la montmonrillonite, la saponite, la beidellite, l'estévensite, l'illite, et des combinaisons de celles-ci, ou de l'argile fibreuse telle que la sépiolite, la palygorskite et des combinaisons de celles-ci, ladite composition pouvant être obtenue par un traitement de carbonisation d'au moins un biopolymère, tel que du chitosane, de l'alginate, de la pectine, de la gomme de guar, de la cellulose, de la gélatine, du collagène, de la zéine, de l'ADN et n'importe laquelle de leurs combinaisons, ledit biopolymère étant associé à au moins une argile. L'invention concerne un procédé d'obtention de ladite composition et son utilisation en tant qu'additif de matrices polymères pour les doter de propriétés électriques, thermoélectriques, en tant que composant dans des supracondensateurs et des électrodes de batteries, en tant que composant de panneaux écrans contre le rayonnement électromagnétique, pour la préparation de composites conducteurs électriques et thermiques par remplissage de la structure poreuse de la mousse à l'aide de polymères.
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ES201130835A ES2393474B1 (es) | 2011-05-23 | 2011-05-23 | Composición de material carbonoso obtenible por carbonización de un biopolímero soportado sobre arcilla. |
ESP201130835 | 2011-05-23 |
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WO2012160229A1 true WO2012160229A1 (fr) | 2012-11-29 |
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PCT/ES2012/070362 WO2012160229A1 (fr) | 2011-05-23 | 2012-05-22 | Composition de matière carbonée pouvant être obtenue par carbonisation d'un biopolymère supporté sur de l'argile |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2015150676A1 (fr) | 2014-03-31 | 2015-10-08 | Institut Français Des Sciences Et Technologies Des Transports, De L'aménagement Et Des Réseaux | Dispositif d'acquisition, procede de fabrication de celui-ci, procede de mesure de force. |
WO2019122475A1 (fr) * | 2017-12-19 | 2019-06-27 | Narbon, S.L. | Composition émotionnelle à base d'argile destinée à une utilisation en tant que reliquaire |
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DE3826452A1 (de) * | 1988-08-04 | 1990-02-08 | Bitzer Diethelm | Tone |
WO2005087854A2 (fr) * | 2003-10-10 | 2005-09-22 | Dow Global Technologies Inc. | Composite d'argile expansee dans la suie et son procede de preparation |
WO2006110137A1 (fr) * | 2005-04-08 | 2006-10-19 | Dow Global Technologies, Inc. | Composite d’argile expanse dans la suite et son procede de preparation |
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2011
- 2011-05-23 ES ES201130835A patent/ES2393474B1/es not_active Expired - Fee Related
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2012
- 2012-05-22 WO PCT/ES2012/070362 patent/WO2012160229A1/fr active Application Filing
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DE3826452A1 (de) * | 1988-08-04 | 1990-02-08 | Bitzer Diethelm | Tone |
WO2005087854A2 (fr) * | 2003-10-10 | 2005-09-22 | Dow Global Technologies Inc. | Composite d'argile expansee dans la suie et son procede de preparation |
WO2006110137A1 (fr) * | 2005-04-08 | 2006-10-19 | Dow Global Technologies, Inc. | Composite d’argile expanse dans la suite et son procede de preparation |
Non-Patent Citations (2)
Title |
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GOMEZ-AVILES, A. ET AL.: "Multifunctional materials based on graphene- like sepiolite nanocomposites.", APPLIED CLAY SCIENCE, vol. 47, 2010, pages 203 - 211 * |
SANTOS BISPO, T. ET AL.: "Semiconductor carbon composite from coir dust and sepiolite.", MATERIALS CHARACTERIZATION, vol. 62, January 2011 (2011-01-01), pages 143 - 147 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015150676A1 (fr) | 2014-03-31 | 2015-10-08 | Institut Français Des Sciences Et Technologies Des Transports, De L'aménagement Et Des Réseaux | Dispositif d'acquisition, procede de fabrication de celui-ci, procede de mesure de force. |
US10989612B2 (en) | 2014-03-31 | 2021-04-27 | Institut Francais Des Sciences Et Technologies Des Transport, De L'amenagement Et Des Reseaux | Sensor with a plurality of acquisition devices that measure force using impedance |
WO2019122475A1 (fr) * | 2017-12-19 | 2019-06-27 | Narbon, S.L. | Composition émotionnelle à base d'argile destinée à une utilisation en tant que reliquaire |
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ES2393474B1 (es) | 2013-11-08 |
ES2393474A1 (es) | 2012-12-21 |
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