BR102017011334B1 - PROCESS FOR SYNTHESIS OF CARBON NANOMATERIALS ON BLAST FURNACE SLAG, PRODUCTS AND USE - Google Patents
PROCESS FOR SYNTHESIS OF CARBON NANOMATERIALS ON BLAST FURNACE SLAG, PRODUCTS AND USE Download PDFInfo
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- BR102017011334B1 BR102017011334B1 BR102017011334-5A BR102017011334A BR102017011334B1 BR 102017011334 B1 BR102017011334 B1 BR 102017011334B1 BR 102017011334 A BR102017011334 A BR 102017011334A BR 102017011334 B1 BR102017011334 B1 BR 102017011334B1
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- Prior art keywords
- synthesis
- blast furnace
- metals
- carbon
- furnace slag
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002893 slag Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 44
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 35
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title claims description 18
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 42
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 38
- 239000004568 cement Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 6
- 238000010276 construction Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 17
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000007792 addition Methods 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007833 carbon precursor Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000003623 transition metal compounds Chemical class 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 238000004320 controlled atmosphere Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000008240 homogeneous mixture Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- -1 transition metal cations Chemical class 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 7
- 238000009472 formulation Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- 239000002717 carbon nanostructure Substances 0.000 description 6
- 229910000805 Pig iron Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000004035 construction material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000007734 materials engineering Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012808 vapor phase Substances 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
- C01B32/15—Nano-sized carbon materials
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- 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
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
a presente invenção trata de um processo de deposição química da fase vapor para a síntese de nanotubos de carbono (ntc) e/ou nanofibra de carbono (nfc) diretamente sobre a escória de alto-forno. tal método produz nanomateriais que podem ser utilizados na formulação de cimento nanoestruturado para a construção civil.The present invention deals with a chemical vapor deposition process for the synthesis of carbon nanotubes (CNT) and/or carbon nanofiber (CNT) directly on blast furnace slag. This method produces nanomaterials that can be used in the formulation of nanostructured cement for civil construction.
Description
[01] A presente invenção trata de um processo de deposição química da fase vapor para a síntese de nanotubos de carbono (NTC) e/ou nanofibra de carbono (NFC) diretamente sobre a escória de alto-forno. Tal método produz nanomateriais que podem ser utilizados na formulação de cimento nanoestruturado para a construção civil.[01] The present invention deals with a chemical vapor deposition process for the synthesis of carbon nanotubes (CNT) and/or carbon nanofiber (NFC) directly on blast furnace slag. This method produces nanomaterials that can be used in the formulation of nanostructured cement for civil construction.
[02] Os nanotubos e nanofibras de carbono atualmente são reconhecidos como um dos materiais mais importantes em nanociência e nanotecnologia e seu emprego é amplo em vários segmentos da engenharia de materiais, biomateriais, na química e petroquímica, na indústria farmacêutica e em medicina. Em particular, a incorporação de NTC a materiais é hoje uma fonte de geração de novos compósitos com propriedades mecânicas muito superiores aos materiais convencionais (Ladeira, L. O et al.Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, 05 de novembro de 2009. PCT/BR2009/000119).[02] Carbon nanotubes and nanofibers are currently recognized as one of the most important materials in nanoscience and nanotechnology and their use is widespread in various segments of materials engineering, biomaterials, chemistry and petrochemistry, the pharmaceutical industry and medicine. In particular, the incorporation of CNTs into materials is today a source of generation of new composites with mechanical properties far superior to conventional materials (Ladeira, L. O et al. Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker , and nanostructured products. WO2009132407, November 5, 2009. PCT/BR2009/000119).
[03] Nanotubos de carbono são nanoestruturas fibrilares de carbono em forma de tubos com diâmetro variando de 0,7 a 50 nm e comprimento variando de 0,5 a 1000 nm. Os átomos de carbono nos NTC são ligados entre si por uma ligação covalente forte formando uma rede hexagonal plana típica da fase grafeno do carbono. Os nanotubos de carbono possuem formato destas folhas de carbono, enroladas, podendo ser de uma simples folha enrolada ou de múltiplas folhas concêntricas enroladas, denominadas nanotubos de carbono de parede simples - NTCPS ou de paredes múltiplas - NTCPM, respectivamente. Esta forte ligação entre os átomos de carbono confere a esse nanomaterial propriedades físicas e químicas excepcionais tais como: grande resistência mecânica, inércia química e grande área superficial específica (Ladeira, L. O. et al. Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, 05 de novembro de 2009. PCT/BR2009/000119).[03] Carbon nanotubes are fibrillar carbon nanostructures in the form of tubes with diameters ranging from 0.7 to 50 nm and lengths ranging from 0.5 to 1000 nm. The carbon atoms in CNTs are linked together by a strong covalent bond forming a flat hexagonal network typical of the graphene phase of carbon. Carbon nanotubes have the shape of these coiled sheets of carbon, which can be a simple rolled sheet or multiple concentric sheets rolled up, called single-walled carbon nanotubes - NTCPS or multi-walled carbon nanotubes - NTCPM, respectively. This strong bond between carbon atoms gives this nanomaterial exceptional physical and chemical properties such as: great mechanical resistance, chemical inertness and large specific surface area (Ladeira, L. O. et al. Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, November 5, 2009. PCT/BR2009/000119).
[04] O módulo de elasticidade dos nanotubos de carbono está na faixa de 1 a 1,8 TPa, o que é muito mais elevado que 800 GPa, típico das fibras de carbono comerciais. Sua tensão de ruptura chega a ser 50 vezes maior que a do aço. Tais propriedades mecânicas dos NTC conferem aos materiais que os contém em sua composição uma melhoria de suas características mecânicas e estruturais (Treacy, M. M. J.; Ebbesen, T. W.; Gibson, J. M. Exceptionally high Young's modulus observed for individual carbon nanotubes. Nature, 381, 678-680 ,1996).[04] The elastic modulus of carbon nanotubes is in the range of 1 to 1.8 TPa, which is much higher than 800 GPa, typical of commercial carbon fibers. Its breaking strength can be 50 times greater than that of steel. Such mechanical properties of CNTs provide the materials that contain them in their composition with an improvement in their mechanical and structural characteristics (Treacy, M. M. J.; Ebbesen, T. W.; Gibson, J. M. Exceptionally high Young's modulus observed for individual carbon nanotubes. Nature, 381, 678- 680, 1996).
[05] Dentre os vários processos de síntese de NTC tem-se o método por deposição química da fase vapor (Chemical Vapour Deposition - CVD), o qual possui maior capacidade para escalonamento. Esse processo funciona basicamente através de decomposição ou pirólise de hidrocarbonetos leves (metano, etileno, acetileno, etc.) como agentes precursores de carbono. Essa decomposição é feita sob atmosfera controlada utilizando principalmente gases inertes como agente de controle do ambiente de síntese e como arraste dos subprodutos de reação. Este sistema de síntese é constituído basicamente de um reator tubular com controladores de temperatura e de vazão dos gases envolvidos no processo (Ladeira, L. O; et al.Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, 05 novembro de 2009. PCT/BR2009/000119).[05] Among the various CNT synthesis processes, there is the method by chemical vapor deposition (CVD), which has greater capacity for scaling. This process basically works through the decomposition or pyrolysis of light hydrocarbons (methane, ethylene, acetylene, etc.) as carbon precursor agents. This decomposition is carried out under a controlled atmosphere using mainly inert gases as an agent to control the synthesis environment and to transport reaction by-products. This synthesis system basically consists of a tubular reactor with temperature and gas flow controllers involved in the process (Ladeira, L. O; et al. Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, 05 November 2009. PCT/BR2009/000119).
[06] Em geral, os processos de síntese de NTC por deposição química da fase vapor ocorrem à pressão atmosférica e a reação de síntese é catalisada com a utilização de metais de transição em forma de nanopartículas ancoradas em um suporte metal-óxido termicamente estável. A função do catalisador é promover uma seletividade na reação de pirólise de modo que ela ocorra preferencialmente na superfície dessas partículas (Ladeira, L. O.et al. Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, 05 de novembro de 2009. PCT/BR2009/000119).[06] In general, CNT synthesis processes by chemical vapor deposition occur at atmospheric pressure and the synthesis reaction is catalyzed using transition metals in the form of nanoparticles anchored in a thermally stable metal-oxide support. The function of the catalyst is to promote selectivity in the pyrolysis reaction so that it occurs preferentially on the surface of these particles (Ladeira, L. O.et al. Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407 , November 5, 2009. PCT/BR2009/000119).
[07] Os suportes clássicos de ancoramento de nanopartículas de metais de transição usados para a síntese de grande eficiência de nanotubos de carbono via deposição química da fase vapor (CVD) são estruturas mesoporosas envolvendo óxidos de grande estabilidade térmica em altas temperaturas, a saber: AI2O3, SiO2, MgO e MO3 ou mistura destes, (Ladeira, L. O, et al.Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, 05 de novembro de 2009. PCT/BR2009/000119).[07] The classic transition metal nanoparticle anchoring supports used for the high-efficiency synthesis of carbon nanotubes via chemical vapor deposition (CVD) are mesoporous structures involving oxides of great thermal stability at high temperatures, namely: AI2O3, SiO2, MgO and MO3 or mixture thereof, (Ladeira, L. O, et al. Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, November 5, 2009. PCT /BR2009/000119).
[08] O cimento do tipo Portland é um aglomerante higroscópico resultante da mistura de silicatos, aluminatos e ferro-aluminatos de cálcio em particulado fino denominado clínquer de cimento ao qual é adicionado gipsita (CaSO4). Durante a fabricação do cimento, parte desse clínquer pode ser substituído por adições minerais. A escória de alto-forno é comumente empregada para substituir parte deste clínquer, trazendo vantagens significativas para o produto (Silva, M.G. Cimentos Portland com adições minerais. In: ISAIA, Geraldo Cechella (Org.) Materiais de construção civil e princípios de ciência e engenharia de materiais. 1v. São Paulo: IBRACON. Cap. 23, p. 761-793,2007).[08] Portland-type cement is a hygroscopic binder resulting from the mixture of calcium silicates, aluminates and ferro-aluminates in fine particles called cement clinker to which gypsum (CaSO4) is added. During the manufacture of cement, part of this clinker can be replaced by mineral additions. Blast furnace slag is commonly used to replace part of this clinker, bringing significant advantages to the product (Silva, M.G. Portland cements with mineral additions. In: ISAIA, Geraldo Cechella (Org.) Civil construction materials and principles of science and materials engineering. 1v. São Paulo: IBRACON. Cap. 23, p. 761-793,2007).
[09] A substituição de escória de alto-forno à moagem do clínquer com gesso apenas é possível porque a escória contém em sua composição os mesmos óxidos do clínquer, mas em quantidades diferentes (Neville, A M. Propriedades do concreto. 2. ed. São Paulo: Pini,828: 1997).[09] The replacement of blast furnace slag for grinding clinker with gypsum is only possible because the slag contains in its composition the same oxides as clinker, but in different quantities (Neville, A M. Properties of concrete. 2. ed . São Paulo: Pini,828: 1997).
[010] A escória de alto-forno é um subproduto da fabricação do ferro gusa. Para a produção do ferro-gusa, os materiais são carregados no alto-forno pela extremidade superior. Os gases resultantes da combustão do coque pré-aquecem os materiais até realizarem as reações de redução do minério. Esses gases seguem em fluxo ascendente e entram em contato com os materiais que têm fluxo descendente, reduzindo e fundindo o minério. Assim, origina-se o ferro-gusa e a escória de alto-forno na parte inferior do forno. A escória de alto-forno é mais leve e fica sobre o ferro- gusa. Com isso, esses materiais são facilmente separados devido à diferença de densidade (Mourão, M.B Associação brasileira de metalurgia e materiais. Introdução à siderurgia. São Paulo: Associação Brasileira de Metalurgia e Materiais, 2007. 428 p.; Rizzo, E.M.S. Introdução aos processos siderúrgicos. São Paulo: Associação Brasileira de Metalurgia e Materiais (ABM), 2005. 150p.).[010] Blast furnace slag is a byproduct of pig iron manufacturing. For the production of pig iron, the materials are loaded into the blast furnace from the upper end. The gases resulting from the combustion of coke preheat the materials until the ore reduction reactions are carried out. These gases flow upwards and come into contact with materials that flow downwards, reducing and melting the ore. Thus, pig iron and blast furnace slag originate in the lower part of the furnace. Blast furnace slag is lighter and sits on top of the pig iron. As a result, these materials are easily separated due to the difference in density (Mourão, M.B Brazilian association of metallurgy and materials. Introduction to steelmaking. São Paulo: Associação Brasileira de Metalurgia e Materials, 2007. 428 p.; Rizzo, E.M.S. Introduction to processes steelworkers. São Paulo: Brazilian Association of Metallurgy and Materials (ABM), 2005. 150p.).
[011] A escória de alto-forno sai do alto-forno na forma de líquido viscoso com temperatura entre 1350 °C e 1500 °C, (John, V.M. et al.Tecnologias e Materiais Alternativos de Construção. São Paulo: Editora da UNICAMP. Cap. 6, p.145-190p,2003).[011] Blast furnace slag leaves the blast furnace in the form of a viscous liquid with a temperature between 1350 °C and 1500 °C, (John, V.M. et al. Technologies and Alternative Construction Materials. São Paulo: Editora da UNICAMP Chapter 6, p.145-190p, 2003).
[012] A escória produzida em alto-forno possui composição típica de aproximadamente 45 % de óxido de cálcio (CaO), 35 % de dióxido de silício (SiO2), 12 % de óxido de alumínio (Al2O3), 5 % de óxido de Magnésio (MgO) e 3 % de outros compostos. A escória de alto-forno de caráter básico possui indicador de hidraulicidade de 1,2, determinado pela relação CaO / SiO2 > 1, (Jacomino, V.M. et al.Controle ambiental das indústrias de produção de ferro-gusa em altos-fornos a carvão vegetal. Belo Horizonte: SEGRAC, 2002. 301p.), que é um valor ideal para ser acrescentado ao cimento sem necessidade de nenhum tipo de ativador.[012] Blast furnace slag has a typical composition of approximately 45% calcium oxide (CaO), 35% silicon dioxide (SiO2), 12% aluminum oxide (Al2O3), 5% aluminum oxide Magnesium (MgO) and 3% other compounds. Basic blast furnace slag has a hydraulicity indicator of 1.2, determined by the CaO / SiO2 ratio > 1, (Jacomino, V.M. et al.Environmental control of pig iron production industries in coal blast furnaces vegetal. Belo Horizonte: SEGRAC, 2002. 301p.), which is an ideal value to be added to cement without the need for any type of activator.
[013] Na literatura relacionada à pesquisa e desenvolvimento tecnológico do cimento existem várias inovações com intuito de melhorar as qualidades do cimento. Em geral, as pesquisas e desenvolvimentos tecnológicos nesta área estão centrados principalmente na incorporação de aditivos nanoestruturados ou surfactantes de modo a aumentar a resistência mecânica, alterar a fluidez ou modificar a velocidade de cura do cimento. Foram encontrados no estado da técnica alguns documentos que descrevem tecnologias e trabalhos científicos correlacionados a cimentos nanoestruturados (Ladeira, L. O.;et al. Process for the continuous, large- scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, 05 de novembro de 2009. PCT/BR2009/000119).[013] In the literature related to cement research and technological development, there are several innovations aimed at improving the qualities of cement. In general, research and technological developments in this area are mainly focused on the incorporation of nanostructured additives or surfactants in order to increase the mechanical resistance, change the fluidity or modify the curing speed of the cement. Some documents were found in the state of the art that describe technologies and scientific works related to nanostructured cements (Ladeira, L. O.; et al. Process for the continuous, large-scale synthesis of carbon nanotubes on cement clinker, and nanostructured products. WO2009132407, 05 de November 2009. PCT/BR2009/000119).
[014] Balaguru e colaboradores mostram que o cimento com adição de objetos em escala nanométrica abre um enorme campo de oportunidades na área de compósitos de ultra-alta resistência. Assim, o cimento Portland nanoestruturado torna-se um material de alta tecnologia quando comparado com seu atual status de um material convencional de construção (Balaguru.P. N, et al. Nano-concrete: possibilities and challenges”, The State University of New Jersey, USA. RILEM Proceedings (2005), 2nd International Symposium on Nanotechnology in Construction (NICOM2), 233-243, 2005).[014] Balaguru and collaborators show that cement with the addition of nanometer-scale objects opens up a huge field of opportunities in the area of ultra-high-strength composites. Thus, nanostructured Portland cement becomes a high-tech material when compared to its current status as a conventional construction material (Balaguru.P. N, et al. Nano-concrete: possibilities and challenges”, The State University of New Jersey, USA. RILEM Proceedings (2005), 2nd International Symposium on Nanotechnology in Construction (NICOM2), 233-243, 2005).
[015] Jiang e colaboradores descrevem o uso de nanotubos de carbono para reforço de cimento mostrando que melhores resultados em aumento de propriedades mecânicas são alcançados com a otimização da dispersão e conexão dos nanotubos à matriz de concreto (Jiang, Xin et al.Carbon nanotubes as a new reinforcement material for modern cement-based binders". Institute of Materials Engineering, University of Siegen, Germany. RILEM Proceedings (2005), 2nd International Symposium on Nanotechnology in Construction (NICOM2) 209-213, 2005).[015] Jiang and collaborators describe the use of carbon nanotubes for cement reinforcement showing that better results in increasing mechanical properties are achieved by optimizing the dispersion and connection of nanotubes to the concrete matrix (Jiang, Xin et al.Carbon nanotubes as a new reinforcement material for modern cement-based binders". Institute of Materials Engineering, University of Siegen, Germany. RILEM Proceedings (2005), 2nd International Symposium on Nanotechnology in Construction (NICOM2) 209-213, 2005).
[016] A adição de nanoestruturas de carbono ao cimento produz melhorias nas matrizes cimentícias, promovendo mudanças na microestrutura de forma a melhorar o desempenho do compósito. Em particular, a adição de 0,05 a 1 % de nanotubos de carbono ao cimento induze um aumento de até 79 % em seu módulo de compressão. A adição de nanotubos de carbono em concentrações na faixa de 0,05 a 1 % ao cimento é um fator impeditivo devido ao custo e limitações em quantidade de fornecimento desse nanomaterial. Resultados referentes à melhoria de propriedades mecânicas são apresentados por Han et al., 2015 (Han, B et al. Review of nanocarbon- engineered multifunctional cementitious composities. Composities: Part A, n.70, p. 69-81, 2015).[016] The addition of carbon nanostructures to cement produces improvements in the cement matrices, promoting changes in the microstructure in order to improve the performance of the composite. In particular, the addition of 0.05 to 1% of carbon nanotubes to cement induces an increase of up to 79% in its compression modulus. The addition of carbon nanotubes in concentrations ranging from 0.05 to 1% to cement is an impediment due to the cost and limitations in the quantity of supply of this nanomaterial. Results regarding the improvement of mechanical properties are presented by Han et al., 2015 (Han, B et al. Review of nanocarbon- engineered multifunctional cementitious composites. Composities: Part A, n.70, p. 69-81, 2015).
[017] No estado da técnica não foi encontrada tecnologia similar utilizando- se do processo de produção de nanotubos de carbono sobre escória de alto-forno propostos no presente pedido.[017] In the state of the art, no similar technology was found using the process of producing carbon nanotubes on blast furnace slag proposed in the present application.
[018] A presente invenção trata do processo de produção em larga escala de nanoestruturas de carbono sobre a escória. A escória de alto-forno na presente invenção é usada como matriz cerâmica para suporte de nanopartículas de metais de transição, cuja função é promover o crescimento em situ dessas nanoestruturas diretamente sobre ela, permitindo assim a produção de um tipo de cimento Portland com nanoestruturas de carbono. O processo aqui descrito pode ser incorporado no processo produtivo convencional de cimento na indústria. O invento propõe, também, como parte do processo de síntese de NTC e NFC sobre a escória de alto-forno, o enriquecimento da escória de alto-forno com metais de transição para a produção deste compósito nanoestruturado de forma integrada ou não à indústria convencional de cimento.[018] The present invention deals with the process of large-scale production of carbon nanostructures on slag. The blast furnace slag in the present invention is used as a ceramic matrix to support transition metal nanoparticles, whose function is to promote the in situ growth of these nanostructures directly on it, thus allowing the production of a type of Portland cement with nanostructures of carbon. The process described here can be incorporated into the conventional cement production process in the industry. The invention also proposes, as part of the NTC and NFC synthesis process on blast furnace slag, the enrichment of blast furnace slag with transition metals for the production of this nanostructured composite whether or not integrated into conventional industry. of cement.
[019] O material nanoestruturado resultante deste processo proposto na presente invenção promove o reforço mecânico da matriz cimentícia tornando-a mais resistente tanto do ponto de vista mecânico quanto ambiental. Este processo descrito na presente invenção gera nanoestruturas de carbono, tais como nanotubos e nanofibras de carbono, com baixo custo de produção. A adição de escória em cimento pode então ser aumentada quando comparada ao cimento com escória devido ao aumento da propriedade mecânica induzida pela presença de nanoestruturas de carbono, o que reduz a quantidade de clínquer, consequentemente reduzindo a emissão de CO2 na produção de cimento. Este fato torna o processo proposto muito vantajoso, por minimizar danos ambientais.[019] The nanostructured material resulting from this process proposed in the present invention promotes mechanical reinforcement of the cementitious matrix, making it more resistant from both a mechanical and environmental point of view. This process described in the present invention generates carbon nanostructures, such as carbon nanotubes and nanofibers, with low production costs. The addition of slag in cement can then be increased when compared to cement with slag due to the increase in mechanical property induced by the presence of carbon nanostructures, which reduces the amount of clinker, consequently reducing CO2 emissions in cement production. This fact makes the proposed process very advantageous, as it minimizes environmental damage.
[020] A Figura 1 representa a micrografia da escória com NTC/NFC. Nesta, observa-se regiões com grande quantidade de materiais nanoestruturado após processo utilizando-se mistura com apenas um óxido.[020] Figure 1 represents the micrograph of the slag with NTC/NFC. In this, regions with a large amount of nanostructured materials are observed after a process using a mixture with just one oxide.
[021] A Figura 2 representa a micrografia da escória com NTC/NFC. Nesta, observa-se regiões com grande quantidade de materiais nanoestruturado após processo utilizando-se mistura com um ou mais óxidos.[021] Figure 2 represents the micrograph of the slag with NTC/NFC. In this, regions with a large amount of nanostructured materials are observed after a process using a mixture with one or more oxides.
[022] A presente invenção trata de um processo de deposição química da fase vapor para a síntese de nanotubos de carbono (NTC) e nanofibra de carbono (NFC), no qual a escória de alto-forno é usada como matriz cerâmica para suporte de nanopartículas de metais de transição (catalisador).[022] The present invention deals with a vapor phase chemical deposition process for the synthesis of carbon nanotubes (CNT) and carbon nanofiber (NFC), in which blast furnace slag is used as a ceramic matrix to support transition metal nanoparticles (catalyst).
[023] Trata-se de um processo de síntese direta de NTC/NFC suportados em escória de alto-forno, que posteriormente podem ser misturados ao cimento através da mistura física, gerando um compósito de nanotubos de carbono/escória de alto-forno/cimento.[023] This is a direct synthesis process of CNT/NFC supported on blast furnace slag, which can later be mixed with cement through physical mixing, generating a composite of carbon nanotubes/blast furnace slag/ cement.
[024] Nesse processo, um gás hidrocarboneto leve passa por um reator onde é decomposto a temperaturas entre 600 a 750 °C. Essa decomposição é catalisada pela presença de nanopartículas metálicas gerando uma concentração local aumentada de carbono o que induz a formação de NTC ou NFC sobre o suporte catalítico e consequentemente quando esse material é sintetizado e misturado ao cimento gera o cimento nanoestruturado.[024] In this process, a light hydrocarbon gas passes through a reactor where it is decomposed at temperatures between 600 and 750 °C. This decomposition is catalyzed by the presence of metallic nanoparticles, generating an increased local concentration of carbon, which induces the formation of CNT or NFC on the catalytic support and consequently, when this material is synthesized and mixed with cement, it generates nanostructured cement.
[025] O método proposto na presente invenção compreende as seguintes etapas: a) Enriquecer a escória de alto-forno em fase sólida e/ou fase líquida com metais ou óxidos ou compostos organometálicos de metais de transição ou sais, compreendendo cátions de metais de transição tais como Ti, Cr, Mn, Cu, Mo, W, Al, Ta, Rh, Pt, Pd, Au, Ir, Ru, Nb, Zr, sendo preferencialmente Fe, Co e Ni; b) Introduzir a escória de alto-forno enriquecida em um reator, de atmosfera controlada e redutora, com a injeção de fontes precursoras de carbono, preferencialmente hidrocarbonetos leves, e um gás inerte como agente carreador e aplicação de altas temperaturas nesse ambiente para a ocorrência da reação de pirólise e consequente síntese de NTC e/ou NFC. c) Submeter o material produzido em “b” a um resfriamento natural.[025] The method proposed in the present invention comprises the following steps: a) Enrich blast furnace slag in solid phase and/or liquid phase with metals or oxides or organometallic compounds of transition metals or salts, comprising transition metal cations. transition such as Ti, Cr, Mn, Cu, Mo, W, Al, Ta, Rh, Pt, Pd, Au, Ir, Ru, Nb, Zr, preferably Fe, Co and Ni; b) Introduce the enriched blast furnace slag into a reactor, with a controlled and reducing atmosphere, with the injection of carbon precursor sources, preferably light hydrocarbons, and an inert gas as a carrier agent and application of high temperatures in this environment for the occurrence of the pyrolysis reaction and consequent synthesis of CNT and/or NFC. c) Subject the material produced in “b” to natural cooling.
[026] Na etapa “a”, o enriquecimento em fase sólida pode ser realizado pela mistura física de metais ou óxidos ou compostos organometálicos de metais de transição às fases resultantes da calcinação dos precursores da escória de alto-forno, preferencialmente os suportes óxidos de metais alcalinos ou metais alcalinos terrosos, aluminosilicatos de metais alcalinos ou alcalinos terrosos, silicatos de metais alcalinos ou alcalinos terrosos, óxidos de metais alcalinos terrosos, metais de transição e semi-metais tais como Al2O3, SiO2, CaO, MgO ou fases decorrentes de misturas destes compostos.[026] In step “a”, solid phase enrichment can be carried out by physically mixing metals or oxides or organometallic compounds of transition metals to the phases resulting from the calcination of blast furnace slag precursors, preferably the oxide supports. alkali metals or alkaline earth metals, aluminosilicates of alkaline or alkaline earth metals, silicates of alkaline or alkaline earth metals, oxides of alkaline earth metals, transition metals and semi-metals such as Al2O3, SiO2, CaO, MgO or phases resulting from mixtures of these compounds.
[027] Na etapa “a”, para o enriquecimento em fase sólida pode-se utilizar uma concentração, em massa, entre 0,1 e 10% dos metais de transição em relação à escória de alto-forno (suporte).[027] In step “a”, for solid phase enrichment, a mass concentration of between 0.1 and 10% of transition metals can be used in relation to blast furnace slag (support).
[028] A incorporação, em fase sólida, de óxidos ou compostos de metais de transição ou mistura deles na etapa “a” pode ocorrer após a produção do clínquer de cimento preferencialmente.[028] The incorporation, in solid phase, of oxides or transition metal compounds or mixtures thereof in step “a” can occur after the production of the cement clinker preferably.
[029] O enriquecimento em fase líquida deve compreender a adição de íons de metais de transição à escória pelas seguintes etapas: i) Dissolução de compostos de metais de transição como soluto, preferencialmente em líquidos orgânicos polares anidros e voláteis como solventes; ii) Mistura da solução obtida em (i) à escória de alto-forno, até se alcançar uma mistura homogênea; iii) Secagem da mistura obtida em (ii) por evaporação do solvente; iv) Calcinação da mistura obtida em (iii) em temperaturas de 200°C a 800°C.[029] Liquid phase enrichment must comprise the addition of transition metal ions to the slag through the following steps: i) Dissolution of transition metal compounds as solute, preferably in anhydrous and volatile polar organic liquids as solvents; ii) Mixing the solution obtained in (i) with blast furnace slag, until a homogeneous mixture is achieved; iii) Drying the mixture obtained in (ii) by evaporation of the solvent; iv) Calcination of the mixture obtained in (iii) at temperatures from 200°C to 800°C.
[030] Os seguintes ânions podem ser utilizados na etapa “a”: sulfatos, nitratos, oxalatos, citratos, fosfatos, acetatos ou compostos organometálicos de metais de transição.[030] The following anions can be used in step “a”: sulfates, nitrates, oxalates, citrates, phosphates, acetates or organometallic compounds of transition metals.
[031] Na etapa “b”, as fontes precursoras de carbono são os hidrocarbonetos leves metano, etileno, propano, acetileno, monóxido de carbono, gás natural, sendo preferencialmente utilizado gás natural. Os gases inertes utilizados como agentes carreadores são nitrogênio, argônio, hélio, sendo preferencialmente o nitrogênio.[031] In step “b”, the carbon precursor sources are the light hydrocarbons methane, ethylene, propane, acetylene, carbon monoxide, natural gas, with natural gas being preferably used. The inert gases used as carrier agents are nitrogen, argon, helium, with nitrogen being preferred.
[032] Na etapa “b”, pode-se utilizar forno, preferencialmente tubular inclinado rotativo (parte central giratória) para um crescimento de modo homogêneo dos nanotubos de carbono sobre o pó da escória pode ser utilizado; além do tempo de residência do pó da escória dentro do forno ser controlado pela variação da inclinação do mesmo.[032] In step “b”, an oven can be used, preferably a rotating inclined tubular (rotating central part) for homogeneous growth of carbon nanotubes on the slag powder; in addition, the residence time of the slag powder inside the furnace is controlled by varying its inclination.
[033] A faixa de temperatura possível deve ser entre 600 a 1400°C, sendo preferencialmente 800°C e a pressão total próxima e superior à pressão atmosférica. A atmosfera deve ser controlada para evitar a entrada de oxigênio do ambiente externo.[033] The possible temperature range should be between 600 to 1400°C, preferably 800°C and the total pressure close to and above atmospheric pressure. The atmosphere must be controlled to prevent the entry of oxygen from the external environment.
[034] O processo de síntese de nanomateriais de carbono proposto na presente invenção compreende uma reação catalítica de síntese “in situ” de nanomateriais sobre a escória de alto-forno.[034] The carbon nanomaterials synthesis process proposed in the present invention comprises a catalytic reaction for the “in situ” synthesis of nanomaterials on blast furnace slag.
[035] O processo proposto na presente invenção produz um compósito nanoestruturado caracterizado por ser constituído de nanomateriais de carbono integrados à escória de alto-forno, resultado do referido processo. Tal compósito pode ser utilizado para a formulação de produtos nanoestruturados.[035] The process proposed in the present invention produces a nanostructured composite characterized by being made up of carbon nanomaterials integrated into blast furnace slag, the result of said process. Such a composite can be used to formulate nanostructured products.
[036] O cimento nanoestruturado, compreendendo o compósito nanoestruturado obtido pelo processo descrito na presente invenção, apresenta melhoria nas propriedades físicas e químicas pela presença de nanoestruturas de carbono integradas à sua estrutura.[036] The nanostructured cement, comprising the nanostructured composite obtained by the process described in the present invention, presents improvement in physical and chemical properties due to the presence of carbon nanostructures integrated into its structure.
[037] Os produtos obtidos através do processo descrito na presente invenção podem ser utilizados em diversas modalidades de obas na construção civil.[037] The products obtained through the process described in the present invention can be used in various types of construction work.
[038] A presente invenção pode ser mais bem compreendida através dos exemplos que se seguem, não limitantes da tecnologia.[038] The present invention can be better understood through the following examples, which are not limiting to the technology.
[039] Dez gramas de escória de alto-forno moída foram misturadas a 1,44 g de Fe2O3, o que gera uma mistura com composição 10% em peso de Fe em relação à massa da escória de alto-forno. A mistura do material foi levada a um reator tipo CVD, durante 30 minutos sobre uma placa de carbeto de silício (SiC). O material foi submetido a uma atmosfera inerte de argônio em um fluxo de 100 sccm e um fluxo de etileno a 40 sccm. Em seguida, o fluxo de etileno é interrompido e a amostra é resfriada até a temperatura ambiente sob fluxo de argônio a 100 sccm. Após o resfriamento, a amostra é retirada do reator. Este processo de síntese foi caracterizado por microscopia eletrônica de varredura para verificar a eficiência do processo, como demonstrado na Figura 1. Nesta figura observa-se a formação de NTC e NFC com diferentes morfologias.[039] Ten grams of ground blast furnace slag were mixed with 1.44 g of Fe2O3, which generates a mixture with a composition of 10% by weight of Fe in relation to the mass of blast furnace slag. The material mixture was taken to a CVD-type reactor for 30 minutes on a silicon carbide (SiC) plate. The material was subjected to an inert argon atmosphere at a flow rate of 100 sccm and an ethylene flow at 40 sccm. Then, the ethylene flow is stopped and the sample is cooled to room temperature under argon flow at 100 sccm. After cooling, the sample is removed from the reactor. This synthesis process was characterized by scanning electron microscopy to verify the efficiency of the process, as demonstrated in Figure 1. In this figure, the formation of CNTs and NFCs with different morphologies is observed.
[040] Dez gramas escória de alto-forno moída foi misturado a 1,44 g de Fe2O3, o que gera uma mistura com composição 10% em peso de Fe em relação à massa da escória de alto-forno. Alternativamente, adicionou-se 0,2 g de Al2O3 que representa uma composição com 0,2% em peso de Al em relação à massa da escória de alto-forno. A seguir, a mistura foi espalhada sobre uma placa de carbeto de silício (SiC) e levada sob atmosfera inerte a 750°C num fluxo de argônio e etileno, respectivamente, de 100 sccm e 40 sccm durante 30 minutos. Em seguida, o fluxo de etileno é interrompido e a amostra é resfriada até a temperatura ambiente sob fluxo de argônio a 100 sccm. Após o resfriamento, a amostra é retirada do reator. Esta amostra foi caracterizada por microscopia eletrônica de varredura e os resultados são mostrados na Figura 2.[040] Ten grams of ground blast furnace slag was mixed with 1.44 g of Fe2O3, which generates a mixture with a composition of 10% by weight of Fe in relation to the mass of blast furnace slag. Alternatively, 0.2 g of Al2O3 was added, representing a composition with 0.2% by weight of Al in relation to the mass of blast furnace slag. Next, the mixture was spread on a silicon carbide (SiC) plate and taken under an inert atmosphere at 750°C in a flow of argon and ethylene, respectively, of 100 sccm and 40 sccm for 30 minutes. Then, the ethylene flow is stopped and the sample is cooled to room temperature under argon flow at 100 sccm. After cooling, the sample is removed from the reactor. This sample was characterized by scanning electron microscopy and the results are shown in Figure 2.
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| BR102017011334-5A BR102017011334B1 (en) | 2017-05-30 | 2017-05-30 | PROCESS FOR SYNTHESIS OF CARBON NANOMATERIALS ON BLAST FURNACE SLAG, PRODUCTS AND USE |
| ARP180101216A AR111920A1 (en) | 2017-05-30 | 2018-05-09 | PROCESS FOR THE SYNTHESIS OF CARBON NANOMATERIALS ON BLAST FURNACE SLAG, ITS PRODUCTS AND THEIR USE |
| PCT/BR2018/050175 WO2018218325A1 (en) | 2017-05-30 | 2018-05-28 | Process for synthesizing carbon nanomaterials on blast-furnace slag, products and use |
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