GB2538568A - Gas absorbing mineral polymer - Google Patents

Gas absorbing mineral polymer Download PDF

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Publication number
GB2538568A
GB2538568A GB1508865.1A GB201508865A GB2538568A GB 2538568 A GB2538568 A GB 2538568A GB 201508865 A GB201508865 A GB 201508865A GB 2538568 A GB2538568 A GB 2538568A
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Prior art keywords
mineral polymer
gas absorbing
gas
weight
mineral
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GB1508865.1A
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GB201508865D0 (en
Inventor
Ihsan Harun
Reid Michael
Bapu Uzair
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ALSITEK Ltd
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ALSITEK Ltd
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Priority to GB1508865.1A priority Critical patent/GB2538568A/en
Publication of GB201508865D0 publication Critical patent/GB201508865D0/en
Priority to PCT/GB2016/051480 priority patent/WO2016189291A1/en
Priority to EP16724963.0A priority patent/EP3328518A1/en
Priority to US15/576,638 priority patent/US20190118160A1/en
Priority to CN201680043098.6A priority patent/CN107847849A/en
Publication of GB2538568A publication Critical patent/GB2538568A/en
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/308—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4533—Gas separation or purification devices adapted for specific applications for medical purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4591—Construction elements containing cleaning material, e.g. catalysts
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00267—Materials permeable to vapours or gases
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A gas absorbing mineral polymer such as a metakaolin-based mineral polymer prepared from a mixture comprising 20 to 30% metakaolin by weight. Preferably, the gas absorbing mineral polymer is a foamed mineral polymer comprising a porous structure of voids on the millimetre or nanometre scale, in diameter. Preferably, the gas absorbing mineral polymer is capable of absorbing gases such as nitrogen oxide (NO) and nitrogen dioxide (NO2), carbon dioxide (CO2) and/or sulphur dioxide (SO2) from the surrounding atmosphere. The mineral polymer material may be formed into different shapes for products or parts of products such as a building material, a building, an item of furniture, a combustion engine, a vehicle, a ventilation system or a respiratory device.

Description

GAS ABSORBING MINERAL POLYMER
The present invention relates to gas absorbing mineral polymers. In particular, the present invention relates to mineral polymers that absorb pollutant gases, for example, oxides of nitrogen (NOx).
Background
There are increasing concerns over air quality and levels of air pollution in the atmosphere, particularly air pollution resulting from human activity.
Air pollution is caused by introduction of particulates, gases or other harmful materials into Earth's atmosphere. These may arise from natural sources such as volcanic activity, or from anthropogenic sources, mainly the burning of fossil fuels. Burning fossil fuels releases pollutant gaseous emissions such as oxides of nitrogen, carbon dioxide, carbon monoxide and sulphur dioxide. Often particulates e.g. carbon are also released.
Generally, air pollutants are either toxic compounds or the precursors to environmental problems such as acid rain deposition and photochemical smog. Exposure to air pollution has been linked to disease and even death in humans and animals, and can be damaging to other living organisms such as crops, to ecosystems and to the natural or built environment.
There is an urgent need for materials that can reduce levels of pollutants in the atmosphere. In particular, there is a need for materials that can reduce levels of pollutant gases in the atmosphere.
The present invention is directed at a gas absorbing mineral polymer that addresses some of the above-mentioned problems.
Summary
According to the present invention, as seen from a first aspect, there is provided a gas absorbing mineral polymer.
Preferably, the gas absorbing mineral polymer is a metakaolin-based mineral polymer. More preferably, the mineral polymer is prepared from a mixture comprising 20 to 30% metakaolin by weight.
Preferably, the gas absorbing mineral polymer comprises a porous structure. In some embodiments, the mineral polymer is a foamed mineral polymer and comprises one or more voids on the millimetre scale, for example between 50pm and 5mm in diameter. The porous structure may comprise one or more voids on the nanometre scale and/or one or more voids on the micrometer scale, for example between 1 gm to 3000 p.m in diameter, preferably between 1 pm to 1000 pm.
According to the present invention, as seen from a second aspect there is provided a metakaolin-based mineral polymer for use as a gas absorber.
Preferably, the metakaolin-based mineral polymer is the metakaolin-based mineral polymer herein described. Preferably, the gas absorbing mineral polymer is capable of absorbing gases such as NO2, NO, CO2 and/or SO2.
According to the present invention, as seen from a third aspect, there is provided use of a gas absorbing mineral polymer as herein described for absorbing one or more pollutant gases. Preferably, the pollutant gases include one or more from the list consisting: NO2, NO, CO2 and/or SO2.
According to the present invention, as seen from a fourth aspect, there is provided a method for preparing a gas absorbing mineral polymer.
According to the present invention, as seen from a fifth aspect, there is provided a product comprising a gas absorbing mineral polymer.
Embodiments of the invention comprising the gas absorbing mineral polymer may include, but are not limited to: a building material, a building, a structure, an item of furniture, a combustion engine, a vehicle, a ventilation system or a respiratory device.
Figures The present invention is described with reference to the accompanying Figures: Figure 1 is a perspective illustration of a gas absorbing mineral polymer product according to an embodiment of the invention; Figure 2 is a cross-sectional illustration of the gas absorbing mineral polymer product of Figure 1; Figures 3 a) and b) show the results of gravimetrical CO2 uptake experiments on foamed and unfoamed samples of the gas absorbing mineral polymer of the present invention; Figure 4 is a photograph of an example reaction tube used for absorption spectroscopy experiments; Figure 5 is a photograph of an embodiment of the invention in the form of a mesh wafer or lattice; Figure 6 is a graph showing the concentration of NO2 in a gas stream with alternating use of a reactor comprising the gas absorbing mineral polymer of the present invention; Figure 7 is a photograph of the results of a visual experiment showing the uptake of NO2 by the mesh wafer of Figure 5; Figure 8 is a photograph of an example set-up of a single pass cell used to measure absorption of NO2 vs mass of mineral polymer.
Detailed Description
According to the invention, as seen from a first aspect, there is provided a gas absorbing mineral polymer. Preferably the mineral polymer is a metakaolin-based mineral polymer.
Surprisingly, it has been found that the mineral polymer of the present invention is able to absorb significant amounts of pollutant gases. It is envisaged that the polymer may find application for making products to be used to control pollution levels.
Even more surprising is the absorption affinity of the gas absorbing mineral polymers for NO2 gas, even at the very low concentrations required to meet environmental standards.
Nitrogen oxides which include nitrogen oxide (NO) and nitrogen dioxide (NO2) are important trace gases that make up the earth's atmosphere.
During daylight hours, NO reacts with partly oxidised organic species (R02) in the troposphere to form NO2. In turn, NO2 is photolysed by sunlight to reform NO.
NO + CH302 -, NO2 + CH3O (Eq. 1) NO2 + sunlight -> NO + 0 (Eq. 2) The oxygen atom formed in Equation 2 goes on to form tropospheric ozone.
As a result of these reactions, the sum of NO and NO2 concentrations ([NO] + [N07]) tends to remain fairly constant i.e. in equilibrium, thus it is convenient to think of the two chemicals as a group; hence they are commonly referred to as "NOx".
NO is short-lived and readily converts to NO2 in the presence of excess free oxygen (02 - 2N0+02->2NO2 (Eq. 3) NOx gases are also combustion products from internal combustion engines and fossil fuel electricity generation. The gasses are poisonous pollutants and have been proved to be 30 dangerous to the health of humans and other mammals.
NOx gasses are also part of the chemical mechanism that produces the air pollution effect known as smog.
Many urban areas and traffic corridors regularly record NOx concentrations that are in excess of the maximum recommended levels, often three or four times higher. The resulting impact on human health is severe with premature death being the most extreme but common outcome in some cities.
Attempts have been made to remove roadside NOx by using the photocatalytic properties of titanium dioxide deployed as a coating or paint to roadside structures (Titanium dioxide photocatalysis, Akira Fujishima, Tata N. Rao, Donald A. Tryk 2000). However, full scale trials have shown that the rate of catalysis is insufficient to make a measurable difference in reducing roadside NOx levels, proving titanium dioxide an impractical solution to the problem.
The gas absorbing mineral polymers of the present invention have been found to absorb significant amounts of NO2 gas. Thus, the mineral polymer of the present invention could be used to reduce or control levels of NOx in the atmosphere (see Equations 1-3) It is envisaged that the gas absorbing mineral polymer of the invention would absorb significant and useful levels of other pollutant gases such as SO2.
For the purposes of this invention, the term "mineral polymer" is synonymous with the term "geopolymer". Mineral polymers are a member of a class of synthetic aluminosilicate polymeric materials. They are formed by reacting, for example via dissolution, an aluminosilicate in an alkaline silicate solution or an acidic medium, which upon condensation (curing) forms a mouldable, homogeneous polymeric product. The raw materials for the preparation of mineral polymers are readily available.
Preferably the mineral polymer is prepared from a mixture comprising 20 to 30% by weight of metakaolin.
The mineral polymer mixture may further comprise 5 to 30% by weight of mica. "Mica" would be known to those skilled in the art and refers to a group of sheet silicate (phyllosilicate) minerals. Common types of mica include biotite, lepidolite, muscovite, phlogopite, zinnwaldite, clintonite etc. Preferably, the mica used in the present invention comprises a muscovite mica. Muscovite mica, otherwise known as common mica, isinglass, or potash mica is a phyllosilicate mineral of aluminium and potassium with formula KAl2(A1Si30m)(F,OH)2, or (KF)2(A1203)3(Si02)6(1-120).
Preferably, the alkali metal silicate is potassium silicate or sodium silicate, most preferably potassium silicate.
Preferably, the alkali metal hydroxide is potassium hydroxide. Mixtures of the alkali metal silicate and alkali metal hydroxide with different cations may be used (e.g. NaOH or KOH).
In some embodiment, fibrous materials, such as mineral fibres, may also be added to the reaction mixture to impart various physical properties, such as improved strength. The term "fibrous material" refers to a material consisting of, comprising or resembling fibres.
Suitable fibrous materials include mineral fibres, carbon fibres, metal-based fibres, glass fibres or polymer-based fibres such as Kevlarml.
Preferably, the mineral polymer of the present invention comprises a porous structure. The term "porous structure" refers to the presence of pores, voids and/or passages within a 20 structure.
The extent and scale of the porous structure depends on the molecular structure of the material, additives used and the method of production. The term 'scale of porosity' refers to the size of the voids and/or passages within the structure e.g. a material where the voids 25 have a maximum dimension in the range 1 to 1000 nm have a nanometre scale of porosity.
Preferably, the gas absorbing mineral polymer is a foamed mineral polymer.
In the context of the present invention, the person skilled in the art would understand what 30 is meant by a foamed mineral polymer and non-foamed mineral polymer.
However, by way of example, a foamed material is a substance (e.g. a particle or other object) that is formed by trapping pockets of gas in a rigid. As a result, a proportion of the internal volume of a foamed substance is a gas such that the density of a substance is lowered the greater the content of gas. A non-foamed material should be substantially free of trapped gas, although small amounts of trapped gas may be present, such as might be introduced from a preparative method.
The foamed mineral polymer material would may contain a network of gaseous voids (cells) throughout its volume which may take an open-or closed-cell arrangement.
In accordance with the present invention, the foamed mineral polymer would preferably have between 5 to 80% of its internal volume consisting of gaseous voids. In preferred 10 embodiments, the foamed mineral polymer may have greater than 5%, and more preferably greater than 10% of its internal volume consisting of gaseous voids.
The term "internal volume" refers to any part of the material defined by the geometrical envelope of a gas absorbing mineral polymer material. Thus, gaseous voids may be enclosed in the material or on the surface of the material. The nanoporous nature of typical geopolymer is shown in Nano-and microporos/ty rn geopolymer gels; JL Bell, M Gordon and WM Kriven, A blowing or foaming agent is used in the preparation of the foamed mineral polymer material. The foaming agent is generally added just before pouring or moulding the material.
Preferably, hydrogen peroxide is used, but finely divided aluminium or other gas producing material may also be used. In the case of hydrogen peroxide, there is a reaction with the alkaline chemistry of the mixture that breaks the hydrogen peroxide down into water and gaseous oxygen. It is the oxygen evolved in the reaction that provides the blowing within the bulk of the material that creates the voids.
Alternatively a gas may be incorporated mechanically e.g. by mixing just as it may with whipped egg whites.
In some embodiments of the invention, the foamed mineral polymers may comprise a structure of porosity on the millimetre scale. That is they have, because of their molecular structure, voids (pores) and/or passages within the structure that are on the millimetre scale, for example, voids with a dimension in the range 50pm and 5mm. This scale of porosity may result from the addition of a blowing agent (foaming stage) in the preparation of the mineral polymer.
Preferably, the foamed mineral polymer materials are also nano-porous. That is they have, because of their molecular structure, voids and/or passages within the structure that are on the nanometre scale, for example, voids with a dimension in the range 0 nm to 1000 nm. Advantageously, such porosity allows small molecules to pass into the apparently solid structure.
In some embodiments of the invention, the foamed mineral polymers may further comprise a structure of porosity on the micrometer scale, for example, having voids with a dimension in the range 1 pm to 3000 pm, preferably 1 p.m to 3000 pm. As an example, it has been found that when the mineral polymers are made from a mixture comprising filler materials, a structure of porosity on a micrometer scale is created.
For example, the gas absorbing mineral polymer may be prepared from a mixture further comprising 35 to 55 % by weight of a filler, preferably 40 to 45% by weight of a filler, more preferably 41.5% by weight of filler.
The nano and microporosity of mineral polymers was investigated in the study; Nano-and inicroporosily in geopolymer gels, JL Bell, M Gordon and WM Kriven, as well as other investigations into the phenomenon.
The implication of the high degree of very fine porosity is an extremely high specific surface area available for absorption in the order of four or five orders of magnitude higher than the flat surfaces of titanium dioxide previously proposed for the purpose of mitigating NOx emissions.
The term "filler" would be understood by those skilled in the art and may be functional fillers or mineral fillers. Organic fillers such as plant materials may also be employed. The filler of the geopolymer foam of the present invention can be selected from any material which already contains pockets, cell or voids of gas or gaseous material. By way of example such fillers include glass microspheres, aeroclays, pearlite, vermiculite etc. In an embodiment, the gas absorbing mineral polymer is prepared from a mixture comprising about 20 -30% by weight of a metakaolin, about 20 -30% by weight of a muscovite mica, about 35 -55% by weight of a filler, about 1 -10 % by weight of an alkali metal hydroxide, up to 100% by weight, which may include one or more fibrous materials.
In another embodiment, the gas absorbing mineral polymer is prepared from a mixture comprising about 23 -28% by weight of a metakaolin; about 22 -27% by weight of a muscovite mica; about 40 -45% by weight of a filler, about 5 -10 % by weight of an alkali metal hydroxide; and about 0.1 -3 % by weight of the blowing agent, up to 100% by weight, which may include one or more fibrous materials.
In another embodiment, the gas absorbing mineral polymer is prepared from a mixture comprising about 25 % by weight of a metakaolin; about 24 % by weight of a muscovite mica; about 41.5 % by weight of a filler, and about 8 % by weight of potassium hydroxide and about 0.3 % by weight of the blowing agent, up to 100% by weight, which may include one or more fibrous materials.
In an embodiment, the gas absorbing mineral polymer is prepared from a mixture comprising 20 to 30% by weight of a muscovite mica, about 35 -50% by weight of an aqueous alkali metal silicate solution (with b to 45% by weight of alkali metal silicate), about 1 -10 (14) by weight of an alkali metal hydroxide, and about 1 -5 % by weight of hydrogen peroxide, up to 100% by weight.
More preferably, the mineral polymer is prepared from a mixture comprising about 23 - 28% by weight of a metakaolin; about 22 -27% by weight of a muscovite mica; about 40 45% by weight of an aqueous alkali metal silicate solution; about 5 -10 % by weight of an alkali metal hydroxide; and about 1 -3 % by weight of hydrogen peroxide, up to 100% by weight.
Even more preferably, the mineral polymer is prepared from a mixture comprising about 25 % by weight of a metakaolin; about 24 % by weight of a muscovite mica; about 41.5 % by weight of an aqueous alkali metal silicate solution; about 8 % by weight of potassium hydroxide (about 29% by weight of alkali metal silicate); and about 1.5 % by weight of hydrogen peroxide.
Preferably, the foamed geopolymer material used in the invention has a density of 0.1 to 0.9 g/cm3, and more preferably 0.3 to 0.8 g/cm'. The density of the foamed geopolymer material may depend on a number of factors, for example, the type and particle size of the filler and the mass of blowing agent added have a significant influence on the density of the resultant mineral polymer material.
Some embodiments of the invention may just have one level and type of porosity e.g. nanoporous. Alternative embodiments may have more than one scale and type of porosity e.g. having voids and/or passages within their structure on a nanometre and/or micrometre and/or a millimetre scale.
The combination of multiple scales or types of porosity mean that mineral polymer materials formed in this way offer a large surface area for the absorption of certain gasses and liquids.
In some embodiments of the invention, the mineral polymer may be prepared from a mixture further comprising talcum. The term "talcum" would be understood by those skilled in the art and include for example soap stone and stearite.
The type of talcum used has been found to have an effect on the homogeneity and size of the pores/voids of the mineral polymer. By varying the amount and type of talcum, it has been found that the size and consistency of the macro level of porosity can be controlled. For example, No chlorite, microcrystalline talc, ultrafine D50 = 1 pm' was found to result in homogeneous and small pore sizes whereas 'No chlorite, microcrystalline talc, fine D50 = 25pm topcut' was found to result in more homogeneous but larger pores.
The addition of talcum also imparts lower density to the foam which advantageously enhances the strength of the product.
In an example embodiment, the foamed mineral polymer is prepared from a mixture comprising 20-30% by weight of metakaolin, 9-16% of mica, 10-20% by weight of a metal silicate preferably potassium silicate, 6-13% by weight of an alkali metal hydroxide and preferably potassium hydroxide, 27-39% water, 0-4% alkali resistant glass fibre, 0.5-6% hydrogen peroxide or no-ferrous metal powder or other blowing agent and 0.5-4% of talcum.
As an example, the mixture may comprise 14.5% by weight potassium silicate, 8.7% by weight of potassium hydroxide, 32.4% water, 25% metakaolin, 12.3% mica, 1.5% alkali resistant glass fibre 3.8% hydrogen peroxide and 1.8% of talcum.
According to the present invention as seen from a second aspect there is provided a mineral polymer for use as a gas absorber.
According to the present invention as seen from a third aspect there is provided use of a gas absorbing mineral polymer as herein described by absorbing NOx/pollutant gases.
According to the present invention, as seen from a fourth aspect, there is provided a method for selective absorption of one or more gases, the method comprising: providing a mineral polymer according to the present invention; exposing said mineral polymer to one or more gases.
Preferably, the one or more gases comprise NOx.
Preferably, NOx is absorbed selectively over other gases present in the atmosphere such as argon, nitrogen, oxygen, ammonia.
According to the present invention, as seen from a fifth aspect, there is provided a product comprising a gas absorbing mineral polymer.
The gas absorbing mineral polymer product may be formed by such techniques as extrusion, additive manufacturing, reaction injection moulding or transfer injection moulding into appropriate shapes to accept pollutant gasses.
A variety of applications and embodiments of the mineral polymer gas absorber according to the present invention are envisaged. The mineral polymer material may be formed into any number of different shapes for products or parts of products with the purpose of absorbing pollutant gases such as NOx. Alternatively, the mineral polymer may be directly incorporated into the design of structures or products such as buildings and vehicles.
It is envisaged that the mineral polymer would be situated for use near to or adjacent the source of the pollution, for example, along a busy road, runway, in or adjacent the exhaust stream of a vehicle engine.
The gas absorbing mineral polymer may be used in the creation of both functional and/or aesthetic structures such as sculptures. It is envisaged that the mineral polymer could be used as an alternative to conventional materials.
The shapes of structures or products made from the gas absorbing mineral polymer may be designed in such a way to maximise the surface area accessible by the target gasses. For example, the products or parts may be formed to provide an "open" structure such that wind may blow through the structure rather than blow around the part.
In some embodiments, the gas absorbing mineral polymer may comprise a three dimensional lattice or mesh of extruded strands of the mineral polymer, for example, see Figures 1 and 2.
The gas absorbing structure 100 illustrated in Figures 1 and 2 may be formed of, for example, a foamed mineral polymer prepared from a mixture comprising about 25 % by weight of a metakaolin (Argical-M 1200S, AGS Mineraux) calcined at approximately 750 °C; about 24 % by weight of a muscovite mica (Imerys M814, Imerys); about 4L5 % by weight of an aqueous potassium silicate solution (Crosfield K66); about 8 '1-1) by weight of potassium hydroxide and about 10.5 % by weight of a blowing agent. alkali metal silicate); and about 10.5 % by weight of the blowing agent.
Alternatively, the structure may be formed of a non-foamed geopolymer material prepared from a bulk mixture consisting of 25% by weight of metakaolin (Argical-M 1200S, AGS Mineraux) calcined at approximately 750 °C; 24% by weight of a muscovite mica (Imerys M814, Imerys); 43% by weight of a 29% by weight aqueous potassium silicate solution (Crosfield K66); and 8% by weight of potassium hydroxide.
The gas absorbing mineral polymer structure 100 is a three dimensional lattice of extruded strands of the mineral polymer of a nominal size. The structure 100 is self-supporting. Further embodiments of the structure 100 (not shown) may comprise additional supporting structures made of a suitable material. Care must be taken when choosing which material to use as an additional support as there are often problems with differential thermal expansivity when attaching mineral polymers to other materials. Mineral polymers are recognised to have the lowest thermal expansivity in a system. The term thermal expansivity is recognised as the tendency of matter to change in volume in response to a change in temperature through heat transfer and this is the interpretation intended.
The purpose of the structure is to provide a solid barrier to roadside wind and breezes that has the strands sufficiently far apart that the air would pass through the structure, rather than passing around it thus presenting a large surface area provided to the air.
Whilst the air passes through the structure the NOx molecules are absorbed and the air therefore purified. Such a lattice may be formed to provide panel, pillar or other shapes, placed by the roadside.
In an alternative embodiment, the gas absorbing mineral polymer may be in the form of rock like or pebble shapes and may be contained within structures such as gabions as part of shoring or landscaping features.
In an embodiment, the gas absorbing mineral polymer of the present invention may be formed as a very thin sheet or ribbon. The sheet would be made as thin as possible to obtain the largest surface area possible per unit of mass without loss of strength necessary to prevent the sheet from being able to support its own weight. As an example, the thickness of the sheet may be in the range 0.2 mm to 4 mm.
Furthermore, it is envisaged that the gas absorbing mineral polymer according to the present invention may be formed in the shape of street furniture, for example, benches, posts, signposts, etc. Alternatively, architectural features of buildings may be provided that comprise the gas absorbing mineral polymer of the present invention.
Alternatively, the gas absorbing mineral polymer may be used in building ventilation systems or in respiratory devices to purify air.
Alternatively the gas absorbing mineral polymer material may be formed into a cartridge for an exhaust system with a multiplicity of gas channels in it.
The absorbed gases may be removed from the mineral polymer either by heating the mineral polymer remotely and capturing the gasses. Alternatively, the absorbed gases may be removed by washing the mineral polymer material either by running water or other liquids, for example, preferably the absorbed gases may be removed from the mineral polymer by rainfall. The gas absorption capabilities of the mineral polymer are thus regenerated.
Materials and Methods Definitions A pollutant gas is a gas whose presence in the atmosphere above a critical level causes harm directly or indirectly to the environment.
The term "mineral polymer" is synonymous with the term "geopolymer". Mineral polymers are a member of a class of synthetic aluminosilicate polymeric materials.
A "foamed mineral polymer" is a mineral polymer comprising trapped pockets or voids of gas. A blowing or foaming agent is used in the preparation of a foamed mineral polymer.
"Metakaolin" would be known to those skilled in the art and refers to a dehydroxylated form of the clay mineral kaolinite.
"Mica" would be known to those skilled in the art and refers to a group of sheet silicate (phyllosilicate) minerals.
A blowing agent, also referred to as foaming agent or gaseous agent may be any blowing agent suitable in the preparation of geopolymer materials including hydrogen peroxide or non-ferrous metals such as aluminium powder or zinc powder.
"Nanoporous material-or "nanoporous structure" refers to a material or structure comprising pores generally 1000 manometers or smaller. IUPAC has subdivided nanoporous materials in to three catergories: microporous (pore size 0.2-2 nm), mesoporous (pore size 2-50 nm) and macroporous (pore size 50-1000 nm).
The term "scale of porosity" refers to the size of the pores, voids and/or passages within a structure e.g. a material comprising a porous structure where the voids have a maximum dimension in the range 0 to 1000 nm have a scale of porosity on the nanometre scale.
The "fibrous material" refers to a material consisting of, comprising or resembling fibres.
The "filler" may be any filler suitable in the preparation of geopolymer materials and may be a functional fillers, mineral fillers or organic fillers such as plant materials.
The "talcum" may be any talcum suitable in the preparation of geopolymer materials.
All terms used throughout the specification unless otherwise defined should be given their everyday meaning as understood by the skilled person.
Experiments To demonstrate the gas absorption capabilities of the mineral polymer of the present invention, gravimetric tests were conducted that showed an affinity of the material with CO2 Figure 3a) shows the uptake of CO2 of a sample of foamed gas absorbing mineral polymer of the present invention.
Figure 3b) shows the uptake of CO2 of a sample of unfoamed gas absorbing mineral polymer of the present invention.
The tests were carried out on samples consisting of ground pieces of mineral polymer foam according the present invention, of between 0.5 mm and 1 mm in diameter. The samples were first heated to 600°C to drive off any already absorbed gasses and then exposed to 100% CO2 at 1 bar, 25°C.
The material picked up 2.18% and 1.3% of its mass respectively for foamed and unfoamed material, in CO2 within a few seconds as shown in Figures 3a) and b) and then became saturated represented by the horizontal portion of the graphs.
The mineral polymer was found to absorb at least 21g CO2 gas per kg of mineral polymer material.
To further investigate the gas absorption capabilities, tests for NO2 absorption were conducted. The mineral polymer material of the present invention was found to have a surprisingly high affinity for NO2 The tests were designed to find out if the material could reduce the concentration levels in the test reactor from an above limit concentration of 50 microgrammes per cubic metre of NO2 to below the limit of 40 microgrammes per cubic metre.
To the surprise of all, the material reduced the concentration not just to below the limit but down below detectable concentrations, that is below t microgramme per cubic metre. Concentrations as low as 40pg/m3 can be reduced down below detectable levels ( Wm') In view of the equilibrium between NO/NO2 gases (Equations 1-3) and since NO in the atmosphere readily converts to NO2, the results of the studies confirm the potential of the gas absorbing mineral polymer to remove NOx gases from the atmosphere.
The following tests were performed: A. Absorption Spectroscopy This test was set up to determine: * Is the mineral polymer capable of reducing the concentration of NO2 in an airflow from a level of 50 p.g/m3 to at least below 40gg/m5? The former figure being over the accepted maximum concentration and a typical roadside level and the latter, the accepted maximum.
* If it is capable of such a concentration reduction, how far below 4Oug/m3 can the material drive the concentration? The apparatus consisted of a glass reaction tube 800mm long and 50mm diameter, see Figure 4. The tube was filled with mesh wafers of the mineral polymer material, see Figure 5.
A flow of air that was loaded with approximately 5Oug/m3 NO2 at 70% relative humidity was introduced at one end of the tube and the output flow from the tube fed into a cavity enhanced absorption spectrometer to measure the output level of NO2.
The graph depicted in Figure 6 shows the three experiments done using this apparatus.
The initial section shows the input gas concentration being fed directly into the spectrometer to verify the concentration (shown here at an average of 43gg/m3).
The second section shows the output concentration at a flow rate of 0.5 litres per minute (1/m). The output concentration is measured to be below detectable limits (2p.g/m3) The third section again confirms the input concentration as the flow rate is increased to I Um. The fourth section again shows the output concentration below detectable limits. The fifth section confirms the input concentration as the flow rate is increased to 1.5 1/m. The sixth section again shows the output concentration below detectable limits. The seventh section is a final confirmation of the input concentration.
These results show a surprisingly high rate of removal of NO2from the airflow, much more than was anticipated when designing the experiment.
Such a powerful absorptive capacity changed what was needed to further explore the approximate level of feasibility of the use of mineral polymer as an absorbent of NO2.
It has been found that the mineral polymer according to the present invention may absorb NO2 at concentrations less than 2µg/m3 and may absorb at least 3g NO2 per kg of mineral polymer material.
A test to indicate the rate of uptake that is possible and also a test to determine whether a significant loading of NO2 into the material was possible was then proposed.
B. Visual Experiments A visual experiment was performed to assess the NO2 concentration required for further quantitative experiments. The results are shown in Figure 7.
The apparatus constituted a pair of 0.51 sealed vessels each containing NO2 at 0.7% concentration and room air at ambient relative humidity (RH). The vessel on the right also contained a piece of gas absorbing mineral polymer weighing 2.599 g.
NO2 is a gas with a reddish-brown colour. NO2 gas was clearly present in both vessels at the start of the test and within four minutes it was visibly reducing in concentration in the vessel containing the gas absorbing mineral polymer. By 9 minutes the characteristic colour is almost completely absent.
The brown colour was visually observed to disappear in the bottle containing the mineral polymer in under 10 minutes (uptake rate ca. 0.07% min').
After 28 minutes, the brown colour had disappeared and gravimetric analysis showed the mass uptake in the piece of mineral polymer to be 0.011g.
This was a crude range finding test but proved very graphically a high removal rate.
C. Absorption of NO2 versus absorbent mass A single pass cell was designed to get an initial order of magnitude for the mass proportion of NO2 that the gas absorbing mineral polymer material was capable of consuming. A smaller glass tube reactor was used to expose NO2 to the absorbent. The setup is shown in Figure 8.
By injecting NO2 into the reactor at varying absorbent masses it was possible to ascertain absorption rates and loading of NO2 into the material. See Table 1 below.
Table 1-Absorption of NO2 versus absorbent mass Comment NO2 Sample Mass NO2(8) Absorbed concentration Mass(g) (g/kg) Volume of gas flowed Initial experiment High NO2 concentration in small absorption cell 48 pg.rml 0.0155 (=1.55%) 0.0078 (=0.78%) 0.0074 (=0.74%) 0.0208 (=2.08%) 89.0 197.6 4.3e-6 2.2e-5 0.136 1.936 (1) 0.0045 2.32 0.136 1.936 (2) 0.0028 1.17 0.136 3.320 0.0022 0.65 0.136 6.168 0.0061 0.98 The single pass cell was made to hold in one instance 1.936g of material. The sample had not been dried or heated beforehand.
NO2 at a concentration of 1.55% in Nitrogen was then passed over the material sample. The result was the absorption of 4.3mg of NO2 which translates to 2.2 g/kg.
Then NO2 at a concentration of 0.78% was passed over the same sample and a further 2.2mg was absorbed, which amounted to a further I.17g/kg equivalent being taken on.
This experiment showed that at least 3.3g/kg could be absorbed but that by no means demonstrated a limit of absorption in fact it showed that more than that was likely to be possible but further testing would be needed to ascertain how much.
Table 1 shows the amount of NO2 absorbed per mass of sample. The figures are not saturation levels but merely the levels reached with the amounts of gas introduced. Therefore in the first injection to the 1.936g sample the loading level was equivalent to 2.328/kg. On the second injection extra loading took place equivalent to 1.17 g/kg more. Clearly the saturation level would be higher than the sum of these.
Table 2 -Absorption Rates Mass Absorber (g) 1.936 (experiment la) 1.936 (experiment 3.320 6.168 -2.089 -1.275 -3.303 -1.074 -0.658 -0.996 Rate const min-1(k) Rate/g. sample -5.589 -0.906 Table 2 shows the uptake rates for different masses of sample. It shows: 1 Uptake rate slows as amount of NO2 already absorbed goes up. Indicating a saturation point.
2. Size of sample is inversely related to uptake rate. Indicating a geometric effect on uptake rate.
D. Manufacturing Methods To understand the feasibility of producing large scale structures for the roadside absorption of NO2 by the gas absorbing mineral polymer, it was necessary to evaluate potential mass manufacturing methods.
One such method that was used at the lab scale to produce the samples that were tested at the University of Leicester was extrusion.
In order to evaluate the basic feasibility of extrusion as a method of mass production a larger scale non-manual method was needed. A vacuum extruder supplied by Lucideon (formerly the Ceramic Research Institute) was used for the trial.
The extrusion trial successfully showed that the technique was very suitable for production of large scale structures from extruded members.
References Titanium dioxide photocatalysis -Akira Fujishima, Tata N. Rao, Donald A. Tryk 2000 Nano-and microporosny in geopolymer gels, IL Bell, M Gordon and W M Kriven

Claims (15)

  1. CLAIMS1. A gas absorbing mineral polymer.
  2. 2. A gas absorbing mineral polymer according to claim 1 where the mineral polymer is metakaolin-based.
  3. 3 A gas absorbing mineral polymer according to claim I or claim 2, prepared from a mixture comprising 20 to 30% metakaolin by weight.
  4. 4. A gas absorbing mineral polymer according to any preceding claim comprising a porous structure.
  5. 5. A gas absorbing mineral polymer according to any preceding claim, wherein the porous structure comprises one or more voids 1 to 1000 nm in diameter.
  6. 6. A gas absorbing mineral polymer according to any preceding claim, wherein the porous structure comprises one or more voids 50p.m and 5mm pm in diameter.
  7. 7. A gas absorbing mineral polymer according to any preceding claim, wherein the porous structure comprises one or more voids 1 gm to 3000 pm in diameter.
  8. A metakaolin-based mineral polymer for use as a gas absorber.
  9. 9. Use of a gas absorbing mineral polymer according to any of claims 1 to 7 for absorbing one or more pollutant gases.
  10. 10. Use of a gas absorbing mineral according to claim 9 wherein the pollutant gas is one or more selected from the group: NOx, CO2, SO2.
  11. 11. A method for preparing a gas absorbing mineral polymer according to any of claims 1 to 7.
  12. 12. A method for selective absorption of one or more gases, the method comprising: providing a mineral polymer according to any of claims 1 to 7; exposing said mineral polymer to one or more gases.
  13. 13. A method according to claim 18 wherein the one or more gases is one or more selected from the group NOx, CO2 and SO2.
  14. 14. A product comprising the gas absorbing mineral polymer according to any of claims 1 to 7.
  15. 15. A product according to claim 14, wherein the product is one selected from the list comprising: a building material, a building, a structure, an item of furniture, a combustion engine, a vehicle, a ventilation system, a respiratory device or a cartridge for an exhaust system.
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GB1508865.1A GB2538568A (en) 2015-05-22 2015-05-22 Gas absorbing mineral polymer
PCT/GB2016/051480 WO2016189291A1 (en) 2015-05-22 2016-05-23 Pollutant-reducing mineral polymers
EP16724963.0A EP3328518A1 (en) 2015-05-22 2016-05-23 Pollutant-reducing mineral polymers
US15/576,638 US20190118160A1 (en) 2015-05-22 2016-05-23 Pollutant-reducing mineral polymers
CN201680043098.6A CN107847849A (en) 2015-05-22 2016-05-23 Reduce the mineral polymer of pollutant

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
GB2557221A (en) * 2016-11-30 2018-06-20 Alsitek Ltd Method for preparing a sorbent comprising a mineral polymer

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US3906076A (en) * 1973-10-03 1975-09-16 Grace W R & Co Process for producing zeolite X molecular sieve bodies
EP0940174A2 (en) * 1998-03-04 1999-09-08 Tosoh Corporation Adsorbent for separating gases
US6183539B1 (en) * 1998-07-01 2001-02-06 Zeochem Co. Molecular sieve adsorbent for gas purification and preparation thereof
EP2103579A1 (en) * 2008-03-19 2009-09-23 Microsols Technologies Crushed glass and metakaolin based road binder
WO2013044016A2 (en) * 2011-09-21 2013-03-28 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Geopolymer resin materials, geopolymer materials, and materials produced thereby

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3906076A (en) * 1973-10-03 1975-09-16 Grace W R & Co Process for producing zeolite X molecular sieve bodies
EP0940174A2 (en) * 1998-03-04 1999-09-08 Tosoh Corporation Adsorbent for separating gases
US6183539B1 (en) * 1998-07-01 2001-02-06 Zeochem Co. Molecular sieve adsorbent for gas purification and preparation thereof
EP2103579A1 (en) * 2008-03-19 2009-09-23 Microsols Technologies Crushed glass and metakaolin based road binder
WO2013044016A2 (en) * 2011-09-21 2013-03-28 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Geopolymer resin materials, geopolymer materials, and materials produced thereby

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2557221A (en) * 2016-11-30 2018-06-20 Alsitek Ltd Method for preparing a sorbent comprising a mineral polymer

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