WO2024076666A1 - Briques à base de charbon à haute résistance et durables et procédés de fabrication de briques à base de charbon - Google Patents

Briques à base de charbon à haute résistance et durables et procédés de fabrication de briques à base de charbon Download PDF

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Publication number
WO2024076666A1
WO2024076666A1 PCT/US2023/034528 US2023034528W WO2024076666A1 WO 2024076666 A1 WO2024076666 A1 WO 2024076666A1 US 2023034528 W US2023034528 W US 2023034528W WO 2024076666 A1 WO2024076666 A1 WO 2024076666A1
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pcb
mixture
clause
samples
water
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PCT/US2023/034528
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English (en)
Inventor
Kam Weng NG
Hua Yu
Chooi Kim Lau
Sahul KHAREL
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University Of Wyoming
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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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017—Aspects relating to the protection of the environment
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]

Definitions

  • Embodiments of the present disclosure generally relate to structural materials.
  • the disclosure relates to pyrolysis char bricks (PCBs) and methods of fabricating PCBs.
  • Coal currently serves an important role as an energy source.
  • an increasing demand for renewable energy has reduced the production and consumption of coal in the United States of America (USA).
  • Coal is carbon-rich, and its use in energy generation may affect atmospheric CO2 levels.
  • the air pollution and global environmental issues associated with the combustion of coal have limited the continuous application of coal in energy production.
  • BSEE Bureau of Safety and Environmental Enforcement
  • a pyrolysis char brick (PCB) is disclosed.
  • the PCB includes a composition.
  • the composition includes a dry mixture and a wet mixture.
  • the dry mixture includes pyrolysis char (PC) and cement materials.
  • the wet mixture includes water, silica fume (SF); and additives.
  • the composition is about 20% to about 40% of PC, about 20% to about 60% cement materials, about 0.1 % to about 10% SF, and about 1 % to about 1 .5% additives, by weight.
  • a pyrolysis char block paver (PCBP) is disclosed.
  • the PCBP includes a composition.
  • the composition includes a dry mixture and a wet mixture.
  • the dry mixture includes pyrolysis char (PC) and cement materials.
  • the wet mixture includes water, silica fume (SF), and additives.
  • the composition is about 25% to about 35% of PC, about 20% to about 60% cement materials, about 0.1 % to about 10% SF, and about 1 % to about 1.5% additives, by weight.
  • a method of forming a PCB includes mixing water and additives to form a wet mixture; mixing pyrolysis char (PC) and cement materials to form a dry mixture; mixing the wet mixture and the dry mixture to form a pyrolysis char brick (PCB) mixture; transferring the PCB mixture to a mold; pre-pressing the PCB mixture; initially curing the PCB mixture to for a PCB; demolding the PCB; and curing the PCB.
  • PC pyrolysis char
  • PCB pyrolysis char brick
  • Figure 1 illustrates a flow diagram of a method of forming pyrolysis char bricks (PCBs), according to embodiments of the disclosure.
  • Figure 2A is a graph illustrating the densities of PCBs with a water/(PC + binder) mass ratios of 0.39, according to embodiments of the disclosure.
  • Figure 2B is a graph illustrating of cubic char specimens for water/(PC + binder) mass ratios of 0.45, according to embodiments of the disclosure.
  • Figure 3A is a graph illustrating the compressive strengths of PCB samples for water/(PC + binder) mass ratios of 0.39, according to embodiments of the disclosure.
  • Figure 3B is a graph illustrating the compressive strengths of PCB samples for water/(PC + binder) mass ratios of 0.45, according to embodiments of the disclosure.
  • Figure 4 is a graph illustrating the densities of PCB samples with different additives, according to embodiments of the disclosure.
  • Figure 5 is a graph illustrating the compressive strengths of PCB samples with different additives, according to embodiments of the disclosure.
  • Figure 6A is a graph illustrating the water absorption percentage of PCB samples, according to embodiments of the disclosure.
  • Figure 6B is a graph illustrating the water absorption saturation coefficient of PCB samples, according to embodiments of the disclosure.
  • Figure 7A is a graph illustrating the heat flow of the PCB mixture samples with a w/c ratio of 0.58, according to embodiments of the disclosure.
  • Figure 7B is a graph illustrating the cumulative heat of the PCB mixture samples with a w/c ratio of 0.58, according to embodiments of the disclosure.
  • Figure 7C is a graph illustrating the heat flow of the PCB mixture samples with a w/c ratio of 0.68, according to embodiments of the disclosure.
  • Figure 7D is a graph illustrating the cumulative heat of the PCB mixture samples with a w/c ratio of 0.68, according to embodiments of the disclosure.
  • Figure 8A is a graph illustrating the thermogravimetric (TG) curve and differential thermal (DT) curve for PCB samples cured at 7 days, according to embodiments of the disclosure.
  • Figure 8B is a graph of illustrating the thermogravimetric (TG) curve and differential thermal (DT) curve for PCB samples cured at 28 days, according to embodiments of the disclosure.
  • Figure 9A is a scanning electron microscope (SEM) micrograph of a G1-2b sample.
  • Figure 9B is a SEM micrograph of a G1-2b-AE sample, according to embodiments of the disclosure.
  • Figure 9C is a SEM micrograph of a G1-2b-GO sample, according to embodiments of the disclosure.
  • Embodiments of the present disclosure generally relate to structural materials.
  • the disclosure relates to pyrolysis char bricks (PCBs) and methods of fabricating PCBs.
  • PCBs pyrolysis char bricks
  • PCBPs pyrolysis char block pavers
  • a method of forming PCBs is disclosed.
  • PC pyrolysis char
  • PCBs PC bricks
  • compositions can include component(s) of the composition, reaction product(s) of two or more components of the composition, a remainder balance of remaining starting component(s), or combinations thereof.
  • Compositions of the present disclosure can be prepared by any suitable mixing process.
  • Embodiments of the present disclosure generally relate to structural materials.
  • the disclosure relates to pyrolysis char bricks (PCBs) and methods of fabricating PCBs.
  • a composition (e.g., a PCB) includes a dry mixture and a wet mixture.
  • the dry mixture includes PC, binder, and additives.
  • the wet mixture includes water and additives.
  • the binder may include cement materials and silica fume (SF).
  • the PCBs may include about 20% to about 40% of PC, about 20% to about 60% cement materials, about 0.1 % to about 10% SF, and about 1 % to about 1.5% additives, by weight.
  • the wet mixture and dry mixture may be mixed together to form a PCB mixture.
  • the water to PC ratio in the PCB mixture is from about 0.5 to about 1 .5.
  • the water to (PC + binder) ratio is from about 0.3 to about 0.5.
  • the PCB mixture when cured, may become the PCBs.
  • the PCBs have a compressive strength from about 5 MPa to about 60 MPa, such as about 35 MPA to about 55 MPa for PCBs with additives.
  • the density of the PCBs is from about 1.0 g/cm 3 to about 2.0 g/cm 3 , such as about 1.3 g/cm 3 to about 1.6 g/cm 3 .
  • the compressive strength of the PCBs with additives is greater than that of a conventional clay brick (about 10 MPa to about 35 MPa), making the PCBs suitable for construction applications.
  • the PCBs may be treated with a hydrophobic coating.
  • the treated PCBs have a water absorption percentage of less than about 5%, such as less than about 3%.
  • the treated PCBs further have a saturation coefficient from about 0.4 to about 1.6, such as about 0.5 to about 0.8.
  • the water absorption percentage and saturation coefficient of treated PCBs was less than that of ASTM C62 Grade Moderate Weathering (MW) brick and ASTM C62 Grade Severe Weathering (SW) brick, making it suitable for use in sever and moderate weather conditions.
  • the additives may include superplasticizers (SPs), air entraining (AE) agents, algae, graphene oxide (GO), or combinations therein.
  • the SF may be amorphous micronized white silicon dioxide pozzolan, a densified SF (e.g., Trinic R-E-D 105WS, Trinic R-E-D 106 pm, Trinic Pozz Plus, Trinic Z3- 95, DMI NanoPozz 100-D), or an undensified SF (e.g., Riteks microfume 106 pm).
  • the GO may be in powder form.
  • the algae may be in liquid form.
  • SP may include polycarboxylic ether polymer (such as BASF Melflux), a polycarboxylate ether, a sulfonated naphthalene formaldehyde, a sulfonated melamine formaldehyde, a lignosulfate, an acrylic polymer, or combinations thereof.
  • the AE agents include acrylic cement modifiers (e.g., Akona liquid), natural wood resins, vinsol resins, synthetic detergents, animal and vegetable fats and oils, water-soluble synthetic organic compounds, alkyl benzene sulfonates, or a combination thereof.
  • the cement materials may include ordinary Portland Cement Type I, ordinary Portland Cement Type II are defined using ASTM C150/C150M (ASTM 2022). Standard sand is defined using ASTM ASTM C33/C33M (ASTM 2018).
  • the PC may include about 75% to about 85% fixed carbon, about 10% to about 20 % ash, about 1 % to about 3% moisture, and about 0.5% to about 1 .5% volatile matter.
  • the PC may be pyrolyzed at between about 800°C and about 900°C.
  • the PCB is a PC block paver (PCBP) having a PC content of from about 25% to about 35%, such as about 30%.
  • PCBP PC block paver
  • the chemical components of PC include fixed carbon (about 80.05%), ash (about 12.93%), moisture (about 7.02%), and volatile matter (about 0.0%).
  • the dimensions of the PCBPs conform to ASTM C936.
  • the density of the PCBPs is about 1 .4 g/cm 3 to about 1 .7 g/cm 3
  • the PCBPs have a compressive strength between about 30 MPa and about 60 MPa, such as about 50 MPa to about 60 MPa.
  • the water absorption of the PCBP is about 4% to about 6%, such as about 4.95%.
  • the PCBPs had an average mass loss of about 15 g/m 2 to about 20 g/m 2 after the freeze thaw test.
  • the abrasion value of the PCBPs was about 2 mm to about 3 mm, such as about 2.25 mm.
  • the abraded volume was about 9 cm 3 to about 13 cm 3 , such as about 10 cm 3 to about 12 cm 3 , such as about 11 .2 cm 3 .
  • FIG. 1 illustrates a flow diagram of a method 100 of forming pyrolysis char bricks (PCBs).
  • PCBs pyrolysis char bricks
  • water and additives are mixed to form a wet mixture.
  • the water and additive may be mixed for about 1 minute to about 10 minutes.
  • the additives may include superplasticizer (SP), silica fume (SF), and graphene oxide (GO).
  • PC pyrolysis char
  • cement materials cement materials
  • sand sand are mixed to form a dry mixture.
  • the PC, cement materials, and sand may be mixed for about 1 minutes to about 5 minutes.
  • the wet mixture is mixed with the dry mixture to form a PCB mixture.
  • the PCB mixture includes about 20% to about 40% of PC, about 20% to about 60% cement materials, about 0.1 % to about 10% SF, and about 1 % to about 1 .5% additives, by weight.
  • the water to PC ratio in the PCB mixture is from about 0.5 to about 1.5.
  • the water to (PC + binder) ratio is from about 0.3 to about 0.5.
  • the wet mixture and the dry mixture may be mixed using a laboratory mixer. The wet mixture and the dry mixture may be mixed for about 1 minute to about 10 minutes.
  • the PCB mixture is transferred to molds.
  • the molds may be metal molds in cubic or brick shape.
  • the PCB mixture is pre-pressed in the mold. The pre-pressing may occur at a pressing pressure of about 4 MPa to about 10 MPa for about 30 seconds to about 3 minutes.
  • the PCB mixture is initially cured to form a PCB.
  • the PCB mixture may be covered with a plastic membrane to prevent moisture loss while being initially cured. After 24 hours of being covered in the plastic membrane, the PCB mixture may be demolded before being initially cured.
  • the PCB mixture may be placed into a wet room with a constant temperature of about 20°C to about 30°C and a relative humidity of about 90% to about 100%.
  • the PCB mixture may be initially cured for about 5 to about 30 days.
  • the PCBs are demolded.
  • the PCBs are transferred to the wet room with a constant temperature of 24°C and relative humidity of 95% to further cure the PCBs. After reaching the designed curing time, e.g., 7, 14, 28 days, the density and compressive strength of PCBs are measured.
  • the PCBs are dried in an oven.
  • the oven dried PCBs may have improved durability and reduced moisture absorption.
  • the PCBs may be oven-dried at 50°C to about 70°C, such as about 60°C, for about 20 hours to about 30 hours, such as about 24 hours.
  • the temperature is set to prevent crystalline water loss in hydration products (e.g., ettringite), which may weaken the bonding between PC and hydration products, and reducing the strength of the PCBs.
  • the PCBs are coated in a hydrophobic coating liquid.
  • the PCBs may be submerged in the hydrophobic coating liquid.
  • a vacuum pressure may be applied for about 20 hours to about 30 hours, such as about 24 hours.
  • the vacuum pressure may enable the filling of pre-existed empty pores in PCBs with the hydrophobic coating liquid.
  • the hydrophobic coating liquid may be a styrene acrylate material (e.g., BEHR PREMIUM Concrete & Masonry Protector & Waterproofer) with pH ranging from about 7 to about 10 and density of 0.99 g/cm 3
  • the PCBs are air-dried.
  • the PCBs are airdried for about 20 hours to about 30 hours, such as about 24 hours.
  • Embodiments of the present disclosure also generally relates to sues of the compositions described herein.
  • Compositions described herein can also be used for various applications.
  • Illustrative, but non-limiting, applications include concrete masonry units such as cinder blocks, breezeblocks, hollow blocks, concrete blocks, construction blocks, Besser blocks, clinker blocks, paver blocks, among other concrete masonry units.
  • the compressive strength of the PCBs was measured using a Forney compression machine.
  • the compression strength of the PCBs was measured using ASTM C67.
  • the laboratory used for mixing is a stand mixer with a capacity of 7 quarts and maximum mixer speed of 900 rotations per minute.
  • Water absorption tests for the PCBs are performed in accordance with ASTM C67 (2021 ).
  • the water absorption tests comprise 24 hours in cold water and 5 hours in boiling water.
  • Freeze-thaw durability tests are performed in accordance with ASTM C67 (2021 ).
  • the water absorption tests for the PCBPs are performed in accordance with ASTM C1645.
  • the desired water absorption is set in accordance with ASTM C936.
  • the freeze thaw test was performed in accordance with ASTM C1645.
  • the abrasion test is performed in accordance with ASTM C418.
  • thermogravimetric analysis and differential thermal analysis was performed using ASTM C1872.
  • thermogravimetric analysis was performed using TA Instruments Q500.
  • PCBs The pyrolysis char bricks (PCBs) in this disclosure are fabricated from PC produced using Powder River Basin (PRB) coal in Wyoming.
  • the coal is pyrolyzed at a temperature of about 850 °C.
  • the predominant chemical components of PC include fixed carbon (about 79.9%), ash (about 16%), moisture (about 2.9%), and volatile matter (about 1.2%).
  • the PC bricks further include ordinary Portland cement type I & II referring to ASTM C150/C150M (ASTM 2022), standard sand referring to ASTM C33/C33M (ASTM 2018), silica fume (SF), black graphene oxide (GO) in powder form, algae (AG), superplasticizer (SP), and air entraining (AE) agent.
  • the SF may be manufactured as RED 105 WS and may be amorphous micronized white silicon dioxide pozzolan. Black GO in powder form and AG in liquid form are manufactured at the University of Wyoming. However such materials are available from other commercial manufacturers.
  • the SP is BASF Melflux 2651 F in light yellowish powder form.
  • the air entraining (AE) agent may be an Akona liquid air entraining admixture in liquid form with an amber color.
  • Table 1 shows a summary of the mixture design by weight percentage of the PCB samples. PCB samples having a water to (PC + binder) ratio of 0.39 were designated Group 1 (G1 ), while PCB samples having a water to (PC + binder) ratio of 0.45 were designated Group 2 (G2).
  • the content of sand, SF, and water/cement ratio was varied throughout the various PCB samples.
  • PC and SF in a fine powder may absorb a greater amount of water during the wet mixing process.
  • the binder includes PC, cement materials, and SF. Water content may be reduced to improve the strength of the PCB.
  • the additives (AE, AG, SF, and GO) may further improve the density and compressive strength of the PCBs.
  • the PCB samples are prepared using the prepressing method. Initially, water and additives are weighed and fully mixed for about five minutes to form the wet mixture. Dry PC, cement materials, and sand are weighed and mixed for about three minutes to form the dry mixture. The wet mixture is then added and mixed with the dry mixture using a laboratory mixer for about five minutes. After wet mixing, the mixture is transferred to metal molds (in cubic or brick shape). Then, the wet mixture is pre-pressed with a pressure of about 7 MPa for about 1 minute. After molding, all specimens are covered with plastic membrane to prevent moisture loss for initial curing.
  • PCB samples After 24 hours, all specimens are demolded and transferred to the wet room with a constant temperature of about 24 °C and relative humidity of about 95%. After reaching the designed curing time, the density and compressive strength of PCB samples are measured. The PCB samples are cured for about 7 days, about 14 days, and about 28 days.
  • the PCB samples are treated to reduce moisture absorption.
  • the PCB samples are oven-dried at about 60 °C for about 24 hours.
  • the temperature is set at about 60 °C to prevent crystalline water loss in hydration products (e.g., ettringite), weakening of the bonding between PC and hydration products, and reduction in the strength performance of char bricks.
  • the oven- dried specimens are submerged in a hydrophobic coating liquid, and a vacuum pressure is applied for about 24 hours to facilitate the filling of pre-existed empty pores in PCBs with the hydrophobic coating liquid.
  • the hydrophobic coating liquid may be BEHR PREMIUM Concrete & Masonry Protector & Waterproofer with pH ranging from about 7 to about 10 and density of about 0.99 g/cm 3 .
  • the vacuum-coated PCBs are air-dried for about 24 hours before testing.
  • Figure 2A is a graph illustrating the densities of PCBs with a water/(PC + binder) mass ratios of 0.39.
  • Figure 2B is a graph illustrating of PCBs for water/(PC + binder) mass ratios of 0.45.
  • Increasing the curing time of the PCBs from 7 days to 28 days, regardless of water/(PC + binder) mass ratios or additions of sand and SF, may increase the density of the PCBs slightly ( ⁇ 8%). The increase may be due to newly formed hydration products in PCBs and water absorption from the wet room.
  • the density of G1 PCBs ranges from about 1.19 g/cm 3 to about 1.46 g/cm 3 .
  • the density of G2 PCBs ranges from about 1 .04 g/cm 3 to about 1 .31 g/cm 3 .
  • the G1 PCBs may have a higher density due to the higher water content and lower content of solids in G2 specimens.
  • Figure 3A is a graph illustrating the compressive strengths of PCB samples for water/(PC + binder) mass ratios of 0.39.
  • Figure 3B is a graph illustrating the compressive strengths of PCB samples for water/(PC + binder) mass ratios of 0.45.
  • Increasing sand content to 39.2% decreases the compressive strength of specimens up to 82%.
  • the higher sand content, which has non-binding characteristics, and lower cement material content may result in the lower compressive strength.
  • the highest compressive strength of 25 MPa is observed in the G1 -2 specimen.
  • Increasing the water/(PC+binder) mass ratio may decrease the compressive strength.
  • the compressive strength of G1 -2 is only 2.4% higher than that of G1-0.
  • the SF may benefit the PCB samples in terms of improved durability and elastic modulus.
  • Table 2 shows a summary of the mixture design of PCB samples with different additives.
  • the mixture design of PCB sample G1 -2b at a reduced w/c of 0.58 is comparable to that of cubic specimen G1 -2.
  • the contents of AE, GO, and AG are set as 0.5% for PCB samples G1 -2b-AE, G1-2b-GO, and G1 -2b-AG, respectively.
  • AE may improve workability of the PCB mixture, and can cause a reduction in the plastic viscosity of the PCB mixture.
  • Increasing the AE content may cause a reduction in the w/c ratio, causing a lower w/c ratio for the G1 -2b-AE PCB sample.
  • Figure 4 is a graph illustrating the densities of PCB samples with different additives.
  • Figure 5 is a graph illustrating the compressive strengths of PCB samples with different additives.
  • the densities of all PCB samples ranges between about 1 .45 g/cm 3 and 1 .50 g/cm 3 .
  • the effect of different additives on the density of PCBs may be limited.
  • the compressive strength of conventional clay bricks (10-35 MPa) when tested in accordance with ASTM C62 (2017) and Indian Standard (IS)1077 (1992) is between about 10 MPa and about 35 MPa. All PCB samples cured for 28 days exhibit compressive strength > 49.2 MPa.
  • specimen G1 -2b-AE exhibits the highest compressive strength of 52.5 MPa.
  • the compressive strengths of G1 -2b-GO and G1 -2b-AG are 14.6% and 9.2% higher, respectively, than that of G1 -2b.
  • the compressive strengths of G1 -2b-G0 and G1 -2b-AG become comparable to that of G1 -2b. Both GO and AG may be helpful in developing the early compressive strength while the strength enhancement from GO and AG may diminish with increasing curing time.
  • Figure 6A is a graph illustrating the water absorption percentage of PCB samples.
  • Figure 6B is a graph illustrating the water absorption saturation coefficient of PCB samples.
  • Table 3 is a summary of the water absorption results of PCB samples.
  • 24-h cold water absorptions range from about 21.5% to about 25%, which is higher than that of clay brick with 4% water absorption.
  • the 5-h boiling water absorptions range from about 27.7% to about 31.7%, which is, on average, 75% higher than that of ASTM Grade SW brick and 36% higher than that of ASTM Grade MW brick.
  • the 5-h boiling water absorption of clay brick is only 6.3%, which is lower than the 17% for the ASTM Grade SW brick and 22% for the ASTM Grade MW brick.
  • the saturation coefficient values are close to that of ASTM Grade SW brick.
  • both the 24-h cold water absorption and the 5- h boiling water absorption values are dramatically lower (> 90%) than those of ASTM Grade SW brick, ASTM Grade MW brick and clay brick.
  • the saturation coefficient may be higher than one due to the 5-h boiling water absorption being relatively lower to the 24-h cold water absorption. No additional boiling water absorption and evaporation of pre-existing water occurred at high temperatures (e.g., about 92°C) after the boiling test occurred.
  • Table 4 is a summary of the freeze-thaw (F-T) test results of the PCB samples.
  • the vacuum treated G1 -2b and G1 -2b-AE experience more than 20 and 10 F-T cycles, respectively, without cracking.
  • the PCBs performed better (10-20 cycles) than the commercial clay bricks, which cracked at 9 cycles.
  • Figure 7A is a graph illustrating the heat flow of the PCB mixture samples with a w/c ratio of 0.58.
  • Figure 7B is a graph illustrating the cumulative heat of the PCB mixture samples with a w/c ratio of 0.58.
  • the PCB mixture samples include a 0.58 w/c unmodified cement sample (Cement), a 0.58 w/c PCB mixture with superplasticizers sample (Cement+1 ,2%SP), a 0.58 w/c G1 - 2b sample, a 0.57 w/c G1 -2b-AE sample, and a 0.58 w/c G1 -2b-GO sample.
  • a first heat flow peak for the 0.58 w/c unmodified cement sample occurs at about 8.5 hours.
  • This first heat flow peak may be due to the initial hydration of tricalcium silicate (C3S).
  • C3S tricalcium silicate
  • the addition of 1 .2% SP increases the first heat flow peak to about 23.8 hrs. This may be due to the polycarboxylate-based SP delaying the dissolution of C3S, thus delaying the formation of portlandite and CSH.
  • Adding 40% PC delays the first heat flow peak to about 51 hours.
  • This addition of PC may enhance the cement material hydration reaction due to the filler effect and nucleation caused by the electrostatic force between negatively charged PC and positively charged particles of the cement material. The delay may also be due to the large amount of free water absorbed by porous PC due to capillary force and the gradual release of absorbed water during cement material hydration.
  • the cumulative heat of the 0.58 w/c G1 -2b is 69% lower than the 0.58 w/c unmodified cement sample and 39% lower than the 0.58 w/c PCB mixture with superplasticizers sample. As the mixing time increases, the cumulative heat of G1 -2b is 32% lower than that of 0.58 w/c unmodified cement sample and 22% lower than that of the 0.58 w/c PCB mixture with superplasticizers sample.
  • Figure 7C is a graph illustrating the heat flow of the PCB mixture samples with a w/c ratio of 0.68.
  • Figure 7D is a graph illustrating the cumulative heat of the PCB mixture samples with a w/c ratio of 0.68.
  • the PCB mixture samples include a 0.68 w/c unmodified cement sample (Cement), a 0.68 w/c PCB mixture with superplasticizers sample (Cement+1 ,2%SP), a 0.58 w/c G1 - 2b sample, a 0.68 w/c G1 -2b-AE sample, and a 0.58 w/c G1-2b-GO sample.
  • the first heat flow peaks are comparable lower for the 0.68 w/c PCB mixture samples are lower than the 0.58 w/c PCB mixture samples.
  • the first heat flow peak for the 0.68 w/c G1 -2b, 0.68 w/c G1-2b-AE, and 0.68 w/c G1-2b-GO samples are between 43 hrs and 47 hrs.
  • the first heat flow peak of the 0.68 w/c G1 -2b, 0.68 w/c G1 -2b-AE, and 0.68 w/c G1-2b-GO samples occurs about 15% faster than the 0.58 w/c G1 -2b, 0.58 w/c G1 -2b-AE, and 0.58 w/c G1 -2b- GO samples.
  • the higher w/c ration therefore, may accelerate the hydration reaction in the PCB matrix at the early period ( ⁇ 72 hrs). This may be due to the higher amount of free water in the mixture.
  • the peak heat flow and cumulative hydration heats are longer and higher, respectively, that the 0.58 w/c G1 -2b and 0.68 w/c G1 -2b samples. This may be due to the surface surfactants in AE partially obstruct the topochemical reaction of cement materials and water molecules, delaying cement material hydration. The nucleation effect may increase the heat release from the hydration acceleration, while the dilution of major compounds in the cement materials may decrease heat release.
  • Figure 8A is a graph illustrating the thermogravimetric (TG) curve and differential thermal (DT) curve for PCB samples cured at 7 days.
  • Figure 8B is a graph of illustrating the thermogravimetric (TG) curve and differential thermal (DT) curve for PCB samples cured at 28 days.
  • the PCBs include G1-2b samples, G1-2b-AE samples, and G1-2b-GO samples. Three peaks may be observed for all PCB samples.
  • the first peak may correspond to the dehydration of cement material hydration products at about 60°C to about 350°C.
  • the second peak may correspond to the dehydroxylation of portlandite at about 400°C to about 500°C.
  • the third peak may correspond to the decarbonation of calcite at about 600°C to about 800°C.
  • the largest peak of the DT curve is typically observed in dehydration temperatures for unmodified cement. For PCB samples cured at 7 days, the largest peak attains at the decarbonation temperatures. This may be due the absorbed water in the porous structures of PC reducing the available amount of free water in the mixture, which may hinder the formation of hydration products due to the delay in the hydration reaction. It may also be due to the higher air containing CO2 trapped in the porous PC during the mixing process.
  • AtV (60-3 50 “C), AJ ( 400-500 »c), and AlV (600-800 °c) are the weight loss of the samples at 60-350 °C, 400-500 °C and 600-800 °C, respectively, from the TG results;
  • W t is the total weight of sample
  • M CH is the molar mass of portlandite (74.09 g/mol)
  • M caicite is the molar mass of calcite (100.09 g/mol)
  • M H20 is the molar mass of water (18.02 g/mol)
  • M cc>2 is the molar mass of carbon dioxide (44.01 g/mol).
  • Table 5 is a summary of the compositions of PCB samples determined by the TG analysis.
  • the bound water content of G1 -2b- AE samples and G1 -2b-GO samples are 1.7% and 3.4%, respectively, higher than that of G1 -2b samples.
  • the calcite contents of G1 -2b-AE samples and G1 -2b-GO samples are 5.4% and 7.5%, respectively, higher than that of G1-2b samples.
  • the G1 -2b-AE samples and G1-2b-GO samples may improve the early strength of the PCBs.
  • the calcite content of G1 -2b-GO samples is 3% lower than that of the sample at 7 days.
  • the G1 -2b samples and G1 -2b-AE samples do not exhibit this behavior. This may be due to the dissolution of calcite.
  • the dissolution kinetics of calcite are related to pH, CO2 pressure, and temperature.
  • the G1 -2b-GO samples may react with hydroxide ions in an alkaline solution and lose its oxygen-bearing groups, facilitating the dissolution of calcite with the reaction of Equation (4):
  • Figure 9A is a scanning electron microscope (SEM) micrograph of a G1 -2b sample.
  • Figure 9B is a SEM micrograph of a G1 -2b-AE sample.
  • Figure 9C is a SEM micrograph of a G1 -2b-GO sample. Few hydration products fill the porous PC in the G1 -2b samples and G1 -2b-AE samples. In contrast, the porous PC in G1 -2b-GO samples are filled with hydration products.
  • oxygen-containing functional groups on the PC surface decrease. The decrease in oxygen-containing functional groups (which may result in fewer hydrogen bonds to water molecules) of the PC pyrolyzed at 850°C may lead to increased hydrophobicity.
  • the hydrophobic surface of PC hinders the formation of hydration products on the surface or in the micropores of the PC.
  • adding GO with the hydrophilic surface in a high pH environment may form a GO film on the porous surface of the PC and may promote the filling of the micropores with hydration products.
  • PCBPs Pyrolysis char block pavers in this disclosure are fabricated from PC produced using Powder River Basin (PRB) coal in Wyoming. The coal is pyrolyzed at a temperature of about 850°C. The predominant chemical components of PC include fixed carbon (about 80.05%), ash (about 12.93%), moisture (about 7.02%), and volatile matter (about 0.0%). The dimensions of the PCBPs conform to ASTM C936. The density of the PCBPs is about 1.4 g/cm 3 to about 1.7 g/cm 3 .
  • the PCBP further include ordinary Portland cement type I & II referring to ASTM C150/C150M (ASTM 2022), silica fume (SF), black graphene oxide (GO) in powder form, algae (AG), superplasticizer (SP), and air entraining (AE) agent.
  • the SF is a NanoPozz100-D, i.e. an amorphous micronized grey silicon dioxide pozzolana.
  • the SP is a BASF Melflux 2651 F in the form of a light yellowish powder.
  • the AE is an Akona liquid air entraining agent with an amber color, which can be used to introduce air bubbles and improve workability, durability, and resistance to freezing and thawing in various construction applications.
  • Table 6 summarizes the mix design for the PCBP samples.
  • the dry mixture including PC and cement materials is combined with water and additive (e.g., SP and SF) to form the PCBP mixture.
  • the dry mixture and wet mixture are mixed for about 3 minutes.
  • the PCBP mixture is placed into molds in three equal layers. Each layer is compacted using a tamping rod for about 15 to about 20 blows. The tamping may increase the compaction and densification of the PCBP mixture in the mold.
  • the compacted PCBP mixture is transferred to a pressing machine. The pressing machine further increases compaction and densification.
  • the PCBP mixture is cured for about 1 day in to the PCBP.
  • the PCBP is demolded from the mold and placed in a humidifying chamber to cure.
  • the humidifying chamber may provide moisture to the PCBP.
  • the PCBP is cured in the humidifying chamber for about 28 days.
  • the cured PCBP is then coated with hydrophobic liquid.
  • the PCBP is dipped in the hydrophobic liquid for about 24 hours under suction. The immersion of the PCBP in the hydrophobic liquid may increase the water resistance properties of the PCBP, as well as increase the freeze thaw durability.
  • the PCBP samples include a 40% PC, 53.5% cement materials, 1.2% SP, and 5.3% SF sample (C40-R), a 40% PC, 53.1 % cement materials, 1.2% SP, 5.3% SF, and 0.4% fiber sample (C40-R-GF), a 40% PC, 52.4% cement materials, 1.2% SP, 5.3% SF, and 1.06% sodium (Na) sample (C40-R- Na), a 40% PC, 52.1 % cement materials, 1.2% SP, 5.3% SF, 1.06% sodium (Na), and 0.3% AE sample (C40-R-Na-AE), a 40% PC, 53.1 % cement materials, a 40% PC, 52.4% cement materials, 1.2% SP, 5.3% SF, and 1.06% sodium (Na) sample (C40-F-Na), a 40% PC, 52.1 % cement materials, 1.2% SP, 5.3% SF, 1.06% sodium (Na), and 0.3% AE sample (C40-F-Na-AE), a 40% PC, 52.1
  • Fine PC is PC in which 98% of the PC particles are less than 300 microns.
  • the PCBP samples have a water to binder ratio of 0.53, except for the S1 -2F-FA and S1-2FO-FA samples which have a water to binder ratio of 0.45.
  • Table 7 shows the compressive strength of the PCBP samples.
  • the C40-R PCBP ample had a compressive strength of 35.43 MPa.
  • the C40-F PCBP sample had a compressive strength of 35.55 MPa, and the C40-FO has a compressive strength of 38.77 MPa.
  • the wet curing approach may have a higher strength than the PCBPs cured in the humidifying chamber.
  • the C35-FO and C30-FO samples have the highest compressive strength.
  • the C35-FO had a compressive strength of 44.15 MPa and the C30-FO had a compressive stress of 57.46 MPa.
  • Table 8 shows the freeze thaw test results.
  • the water absorption test were conducted on the C30-FO samples. A total of three half-block paver samples were tested. The water absorption of the C30-FO samples was about 4.95%.
  • the freeze thaw was performed to test the ability of the PCBPs to resist crack formation due to extreme cold weather.
  • the freeze thaw test was conducted on three C30-FO samples. A total of 28 cycles were carried out on the PCBP samples. Following the cycles, the residue collected was separated using a filter paper and oven dried. The ratio of the weight of the residue collected to the total surface area results in the average mass loss of the samples.
  • the PCBPs had an average mass loss of about 18.68 g/m 2 , which is within the acceptable limit of 225 g/m 2 as per ASTM C1645.
  • Table 9 shows the abrasion test results.
  • the abrasion test was performed to characterize the PCBPs ability to perform under high abrasive forces, such as moving vehicles.
  • the abrasion test was conducted on two C30- FO samples.
  • the abrasion test was performed on 8 areas of the PCBP as per ASTM C418. A steel plate having a circular perforation at its center was used to expose the testing areas.
  • the abrasion value of the PCBPs was about 11 .2 cm 3 .
  • a pyrolysis char brick including: a composition, the composition comprising: a dry mixture, comprising pyrolysis char (PC); and cement materials; and a wet mixture, comprising: water; silica fume (SF); and additives; wherein the composition is about 20% to about 40% of PC, about 20% to about 60% cement materials, about 0.1 % to about 10% SF, and about 1 % to about 1 .5% additives, by weight.
  • the additives include a superplasticizer (SP), the SP includes polycarboxylic ether polymer, a polycarboxylate ether, a sulfonated naphthalene formaldehyde, a sulfonated melamine formaldehyde, a lignosulfate, an acrylic polymer, or combinations thereof.
  • SP superplasticizer
  • the SP includes polycarboxylic ether polymer, a polycarboxylate ether, a sulfonated naphthalene formaldehyde, a sulfonated melamine formaldehyde, a lignosulfate, an acrylic polymer, or combinations thereof.
  • the additives include an air entraining (AE) agent
  • the AE agent includes acrylic cement modifiers, natural wood resins, vinsol resins, synthetic detergents, animal and vegetable fats and oils, water-soluble synthetic organic compounds, alkyl benzene sulfonates, or a combination thereof.
  • a pyrolysis char pave block comprising: a composition, the composition comprising: a dry mixture, comprising pyrolysis char (PC); and cement materials; and a wet mixture, comprising: water; silica fume (SF); and additives; wherein the composition is about 25% to about 35% of PC, about 20% to about 60% cement materials, about 0.1 % to about 10% SF, and about 1 % to about 1 .5% additives, by weight.
  • PCBP pyrolysis char pave block
  • a method of forming a composition comprising: mixing water and additives to form a wet mixture; mixing pyrolysis char (PC) and cement materials to form a dry mixture; mixing the wet mixture and the dry mixture to form a pyrolysis char brick (PCB) mixture; transferring the PCB mixture to a mold; pre-pressing the PCB mixture; initially curing the PCB mixture to for a PCB; demolding the PCB; and curing the PCB.
  • PC pyrolysis char
  • PCB pyrolysis char brick
  • Clause 30 The method of clause 28, further comprising coating the PCBs in a hydrophobic coating liquid.
  • Clause 31 The method of clause 28, wherein the composition is about 20% to about 40% of PC, about 20% to about 60% cement materials, about 0.1 % to about 10% SF, and about 1 % to about 1.5% additives, by weight.
  • Clause 32 The method of clause 28, wherein the composition has a water to PC ratio (w/c) of about 0.5 to about 1 .5.
  • Clause 33 The method of clause 28, wherein the water and additive are mixed for about 1 minute to about 10 minutes.
  • AE agent includes acrylic cement modifiers, natural wood resins, vinsol resins, synthetic detergents, animal and vegetable fats and oils, water-soluble synthetic organic compounds, alkyl benzene sulfonates, or a combination thereof.
  • Clause 38 The method of clause 28, wherein the cement materials and SF form a binder, and wherein the composition has a PC to binder ratio of about 0.3 to about 0.5.
  • Clause 39 The method of clause 28, wherein the wet mixture and the dry mixture are mixed for about 1 minute to about 10 minutes.
  • Clause 40 The method of clause 28, wherein the pre-pressing has a pressing pressure of about 4 MPa to about 10 MPa.
  • Clause 41 The method of clause 28, wherein the pre-pressing has a pressing time of about 30 seconds to about 3 minutes.
  • Clause 42 The method of clause 28, wherein the temperature of the initial curing is about 20°C to about 30°C.
  • Clause 43 The method of clause 28, wherein the humidity of the initial curing is about 90% to about 100%.
  • Clause 44 The method of clause 28, wherein the initial curing is about 5 to about 30 days.
  • Clause 46 The method of clause 28, wherein the PCB is cured for about 5 days to about 30 days.
  • Clause 47 The method of clause 28, further comprising airdrying the PCB at a temperature of about 50°C to about 70°C
  • Clause 48 The method of clause 47, wherein the PCB is airdried for about 20 hours to about 30 hours.
  • Clause 49 The method of clause 30, wherein the hydrophobic coating includes a styrene acrylate material.
  • compositions, process operation, process operations, an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “Is” preceding the recitation of the composition, process operation, process operations, element, or elements and vice versa, such as the terms “comprising,” “consisting essentially of,” “consisting of” also include the product of the combinations of elements listed after the term.
  • the recitation of the numerical range 1 to 5 includes the subranges 1 to 4, 1.5 to 4.5, 1 to 2, among other subranges.
  • the recitation of the numerical ranges 1 to 5, such as 2 to 4 includes the subranges 1 to 4 and 2 to 5, among other subranges.
  • within a range includes every point or individual value between its end points even though not explicitly recited.
  • the recitation of the numerical range 1 to 5 includes the numbers 1 , 1.5, 2, 2.75, 3, 3.80, 4, 5, among other numbers.
  • every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Des modes de réalisation de la présente divulgation concernent des briques de charbon de pyrolyse (PCB) et des procédés de formation de PCB. La PCB comprend une composition comprenant un mélange sec et un mélange humide. Le mélange sec comprend un charbon de pyrolyse (PC) et des matériaux de ciment. Le mélange humide comprend de l'eau, des fumées de silice (SF) et des additifs. La composition est d'environ 20 % à 40 % de PC, d'environ 20 % à 60 % de matériaux de ciment, d'environ 0,1 % à 10 % de SF, et d'environ 1 % à 1,5 % d'additifs, en poids. Le procédé de formation d'une PCB consiste à mélanger de l'eau et des additifs pour former un mélange humide; à mélanger du charbon de pyrolyse (PC) et des matériaux de ciment pour former un mélange sec; à mélanger le mélange humide et le mélange sec pour former un mélange de brique de charbon de pyrolyse (PCB); à transférer le mélange de PCB dans un moule; à prépresser le mélange de PCB; à durcir initialement le mélange de PCB pour former une PCB; à démouler la PCB; et à durcir la PCB.
PCT/US2023/034528 2022-10-05 2023-10-05 Briques à base de charbon à haute résistance et durables et procédés de fabrication de briques à base de charbon WO2024076666A1 (fr)

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Citations (6)

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US20220298073A1 (en) * 2021-03-18 2022-09-22 Alliance For Sustainable Energy, Llc Cementitious biochar compositions and methods of making the same
US20230002276A1 (en) * 2021-07-02 2023-01-05 HeroSand, LLC Carbon negative concrete production through the use of sustainable materials
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