WO2017017618A1 - Matériaux de silice hybride à base de poss fonctionnalisé en tant que sorbants régénérables hautement efficaces pour capturer le co2 - Google Patents

Matériaux de silice hybride à base de poss fonctionnalisé en tant que sorbants régénérables hautement efficaces pour capturer le co2 Download PDF

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WO2017017618A1
WO2017017618A1 PCT/IB2016/054474 IB2016054474W WO2017017618A1 WO 2017017618 A1 WO2017017618 A1 WO 2017017618A1 IB 2016054474 W IB2016054474 W IB 2016054474W WO 2017017618 A1 WO2017017618 A1 WO 2017017618A1
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silane
sorbent
hybrid silica
adsorption
poss
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PCT/IB2016/054474
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Saraladevi Abhilash KOCHUKUNJUADISSER
Thomas DEEPTHI
Sadhana RETNAKUMARIAMMA
George BENNY KATTIKANAL
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Indian Space Research Organisation
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    • 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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3491—Regenerating or reactivating by pressure treatment
    • 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
    • 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
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4566—Gas separation or purification devices adapted for specific applications for use in transportation means
    • B01D2259/4575—Gas separation or purification devices adapted for specific applications for use in transportation means in aeroplanes or space ships
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • 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

Definitions

  • the present application pertains to the field of development of sorbents for the regenerative removal of C0 2 , and more specifically relates to a functionalized polyhedral oligomeric silsesquioxane (POSS) based hybrid silica as regenerable sorbent materials for C0 2 removal from dilute and ultra-dilute environments, and a method for their production.
  • PES polyhedral oligomeric silsesquioxane
  • Amine species can either be immobilized by wet impregnation or grafted on to substrates, poly(methylmethacrylate) (PMMA), fumed silica, SBA-15, SBA-16, MCM-41, MCM-48, carbon molecular sieves etc are the commonly used substrates and monoethanolamine, diethanolamine (DEA), triethanolamine (TEA) polyethylene imine (PEI), tetraethylene pentamine (TEPA) etc are among the preferred amines used for impregnation.
  • PMMA poly(methylmethacrylate)
  • fumed silica SBA-15, SBA-16, MCM-41, MCM-48, carbon molecular sieves etc are the commonly used substrates and monoethanolamine, diethanolamine (DEA), triethanolamine (TEA) polyethylene imine (PEI), tetraethylene pentamine (TEPA) etc are among the preferred amines used for impregnation.
  • DEA diethanolamine
  • TEPA tetraethylene pentamine
  • Amino silanes can be covalently grafted onto the intrachannel surface of the mesoporous silica through silylation but the preparation of mesoporous material using templates is energy intensive and modification of mesoporous silica by grafting does not yield material with uniform amine distribution throughout the pores.
  • the other approach to synthesize amine grafted adsorbent is the direct synthesis via the co- condensation of two organo silanes, one of which is having amine functionality, in the presence of an organic template using acid or base catalyst.
  • the complete removal of template without calcination is still a difficult problem.
  • US Patent No. 8491705 B2 describes a method for capturing C0 2 from ambient air by the use of solid tethered amine adsorbents, where the amine adsorbents are tethered to a substrate selected from the group of silica, metal oxides and polymer resins.
  • US Patent Application No. 20110150730 describes C0 2 sorbents comprised of mesoporous silica functionalized with polyamine obtained by the in-situ polymerization of azetidine.
  • US patent No. 6547854 Bl describes an amine enriched solid sorbent prepared by treating a solid substrate with acid or base and subsequent or simultaneous treatment with a substituted amine salt for capturing C0 2 .
  • the limitation of the method is its lower adsorption capacity.
  • an object of the present application is to provide an easy, environmentally benign, less energy intensive, and cost effective method for producing functionahzed POSS based hybrid silica as regenerable sorbent material for C0 2 removal.
  • Yet another object of the invention is to provide a versatile sorbent for C0 2 removal from environments of dilute to ultra dilute C0 2 concentration, which is less corrosive, less susceptible to degradation, and provides faster adsorption and desorption and also has high cyclic utility for C0 2 removal.
  • the present invention provides functionahzed POSS-hybrid silica based materials as regenerable sorbents for removal of C0 2 from dilute as well as ultra- dilute environments.
  • the present application provides a process for producing functionahzed polyhedral oligomeric silsequioxane (POSS)-hybrid silica based sorbent materials comprising the steps of:
  • the method of the present invention does not employ any external catalysts, templates and surfactants in the preparation of sorbent.
  • Figure 1 represents the functionalized polyhedral oligomeric silsesquioxane molecule
  • Figure 2 shows the SEM image of functionalized POSS hybrid silica sorbent material synthesized
  • Figure 3 shows the X-ray diffraction pattern of functionalized POSS hybrid silica
  • Figure 4 shows a representation of thermal stability of the material
  • Figure 5 represents the C0 2 adsorption of functionalized POSS hybrid silica sorbent in different C0 2 partial pressures
  • Figure 6 represents the C0 2 adsorption of functionalized POSS hybrid silica sorbent from dry air
  • Figure 7 represents the C0 2 desorption by functionalized POSS hybrid silica sorbent at different temperatures
  • Figure 8 represents the cyclic capability of functionalized POSS hybrid silica sorbent in 100% C0 2
  • Figure 9 represents the cyclic capability of functionalized POSS hybrid silica sorbent in dry air.
  • Table 2 Effect of ageing the silane mixture on C0 2 adsorption.
  • Table 3 Effect of dilution of aged silane mixture on C0 2 adsorption.
  • Table 5 shows the temperature dependence of C0 2 adsorption of the sorbent material.
  • Table 6 shows the C0 2 adsorption efficiency and other characteristics of the resulting sorbent materials of examples 1, 2 and 3.
  • the present invention provides functionalized POSS-hybrid silica based materials as regenerable sorbents for removal of C0 2 from dilute as well as ultra- dilute environments.
  • the functionalized POSS-hybrid silica based sorbents of the present invention comprise of a mixture of an amino silane and an organo silane in a ratio of 1: 1 to 1 :2.
  • the sorbents complete >75% of C0 2 desorption by heating at 60 °C or by vacuum or a by the combination of both temperature and vacuum, and desorbs C0 2 completely by heating at 80 °C or by vacuum or by the combination of both temperature and vacuum.
  • the sorbents are less sensitive to moisture and show a maximum of 1.0 wt% adsorption upon saturation. They have a BET surface area ⁇ 1.4 m 2 /g and particle size in the range of 0.5 to 3.5 microns.
  • the functionalized POSS-hybrid silica based sorbents may be applied for C0 2 capture from atmospheric air, industrial effluent gas streams and closed habitats like space craft crew cabin or submarines.
  • the present application provides a simple, untemplated and self catalyzed method for producing functionalized POSS-hybrid silica based sorbent materials for C0 2 removal comprising:
  • Preparation of the mixture of amino silane and another organo silane involves co- condensation reaction of the amino silane and the organo silane to produce sorbent materials.
  • the general scheme for the hydrolysis of silanes and co-condensation may be shown as follows where R represents an organic moiety.
  • two different organo silanes are co- condensed in the presence of absolute alcohol/water mixture (10: 1 to 20: 1 v/v).
  • Suitable alcohols which may be used include, but are not limited to ethanol, methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and tert butanol, preferably ethanol.
  • the organic functionality (R in FIG. 1) is alkyl amino group which can be primary or secondary or a mixture of the two and the other organic functionality (X in FIG. 1) may be selected from the group of methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, vinyl, allyl, methacryl, cyclopentyl, cyclo hexyl, octyl, phenyl, naphthyl, methacryloxy propyl and combinations thereof.
  • Amino silanes which can be employed for the purposes of the present invention include, but are not limited to amino propyl triethoxy silane, amino propyl trimethoxy silane, N-[(3-trimethoxysilyl)propyl] ethylenediamine, N-[(3-trimethoxysilyl) propyl]diethylenetriamine, and N, N -dimethylaminopropyl) -trimethoxy silane.
  • Suitable organo silanes which can be employed for the purposes of the present invention include but are not limited to vinyl triethoxy silane, vinyl trimethoxy silane, allyl triethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane and methacryloxy propyl trimethoxysilane.
  • the ratio of the aminosilane to the organo silane may range from 1:0.5 to 1 :8, or from 1 : 1 to 1:2.
  • the mixture is prepared suitably by stirring at ambient temperatures for about 20 to 200 minutes, or from about 45 to 180 minutes.
  • the molar concentration of silane/alcohol/water in the mixture is 1 :30:8 in the final solution and may be varied in the range of about 1 :25:5 to 1 :35: 12.
  • the mixture is suitably aged at temperatures ranging from about 15 to 40 °C for about 2 to 10 days, preferably from about 5 to 10 days.
  • the aged silane solution is diluted to about 1 to 50 times of the original concentration in a suitable solvent.
  • suitable solvents for the dilution of the aged silane solution include but are not limited to methanol, ethanol, acetone, propanol and tetrahydrofuran.
  • Spray deposition of the diluted solution to prepare the sorbent silica materials may be carried out by using spray gun at ambient temperatures.
  • the solid product obtained may be dried in an oven under vacuum at a temperature ranging from 65 to 150 °C, more preferably from about 65 to 95 °C under inert gas flow for 8 to 12 hrs.
  • the method of the present application is less expensive, simple and environment friendly for synthesizing the sorbents.
  • the morphology of the obtained material was revealed by field emission scanning electron microscopy (FESEM) analysis (FIG. 2) which showed sphere like particles of 0.5-3.5 ⁇ size.
  • FESEM field emission scanning electron microscopy
  • the crystalline characteristics of the material were revealed by XRD data in FIG. 3.
  • the two reflections appeared at -8° and -22° 2 ⁇ , corresponding to the d-spacing of 10A° and 4.1A° respectively, which are characteristic of POSS.
  • the materials gave a BET surface area of ⁇ 1.4 m 2 /g.
  • the thermal stability of the sorbents was studied by thermogravimetric analysis (FIG. 4) which showed thermal stability up to 300 °C under inert atmosphere.
  • T d * T d (5%) is the temperature for 5% weight loss in thermo gravimetric analyzer
  • the silane mixture After ageing the silane mixture, it was diluted in a suitable solvent to 1 to 50 times.
  • the dilution of aged silane solution may be carried out with a solvent selected from a group of methanol, ethanol, acetone, propanol and THF.
  • the diluted solution upon spray deposition using spray gun at ambient temperature produced POSS-hybrid silica materials of required C0 2 adsorption/desorption properties. It was found that an optimum dilution is essential to get material with maximum C0 2 adsorption as shown in Table 3.
  • the material formed is vacuum dried at a temperature ranging from 50 to 90°C for 8 to 12 hrs.
  • the material was pre-heated between 65 to 150 °C, or from 100 to 150 °C under inert gas flow.
  • Pre heating before C0 2 adsorption is a critical step in the adsorption process as evident from Table 4.
  • the present application provides a method for removal of C0 2 , by adsorption of C0 2 on polyhedral oligomeric silsesquioxane (POSS) based hybrid silica.
  • PPS polyhedral oligomeric silsesquioxane
  • the co-condensation reaction of amino silane and another organo silane produces sorbent materials with organic functionalities capable of C0 2 adsorption.
  • the ratio of amino and other organo silane may be varied suitably to obtain the sorbent material with required properties for C0 2 adsorption.
  • Spray deposition of suitably diluted aged silane solution using spray gun produces functionalized POSS based hybrid silica materials capable of C0 2 adsorption in good yield.
  • the C0 2 adsorption is fast and the material can easily be regenerated at low temperatures.
  • the sorbent materials synthesized were analyzed for C0 2 adsorption capacity using thermo gravimetric analyzer. About 10 mg of the sorbent material was taken in the pan and was heated to 150 °C under the flow rate of 30 mL/min for 15 min. After this pre-conditioning, gas was switched over to dry C0 2 (100%) at a flow rate of 100 mL/min at 30 °C. The material showed a maximum C0 2 adsorption of 10.0 + 0.5 wt% in 100 min.
  • the sorbents were evaluated for the adsorption of C0 2 from 10% C0 2 (balance N 2 ) also.
  • the materials showed a maximum adsorption of 7.6 + 0.5 wt% in 100 min at a flow rate of 100 mL/min at 30 °C.
  • the material is showing fast adsorption kinetics at the initial stage and reaction with C0 2 is continued further at a slower rate.
  • the comparison of adsorption of 100% C0 2 and 10% C0 2 under dry conditions at 30 °C given by TAHSM, in 60 min is given in FIG.5.
  • the moisture adsorption by the sorbent materials were also evaluated by the TG analyzer using He flow (20 ml/min) saturated with moisture using a water saturator.
  • the sorbent materials showed a maximum of 1% moisture adsorption upon saturation at 30 °C showing it's less sensitivity to moisture.
  • the sorbents were evaluated for the adsorption of C0 2 from air under dry and ambient conditions using thermo gravimetric analyzer. The materials showed C0 2 adsorption of 6.0 + 0.6 wt% and 6.0 + 0.5 wt% respectively in dry (400 ppm C0 2 ) and ambient air (400 ppm C0 2 in 60% humidity) at 30 °C in 24 hours.
  • Example-1 Preparation of the sorbent material using N-[(3-trimethoxysilyl) propyl] diethylenetriamine (TAS) and vinyl triethoxy silane (VS).
  • TAS N-[(3-trimethoxysilyl) propyl] diethylenetriamine
  • VS vinyl triethoxy silane
  • TAS N-[(3-trimethoxysilyl) propyl] diethylenetriamine
  • VS vinyl triethoxy silane
  • TAHSM Triamine based Hybrid Silica Material
  • DAS N-[(3-trimethoxysilyl) propyl] ethylenediamine
  • VS ethylenediamine
  • Fixed volume of the aged silane solution was diluted 7 times in absolute ethanol.
  • the diluted solution upon spray deposition at ambient temperature using spray gun produced the material and was vacuum dried at 80 °C for 12 hours.
  • the resultant material was termed as DAHSM (Diamine based Hybrid Silica Material) and its characteristics are shown in Table 6.
  • Example-3 Preparation of the sorbent material using aminopropyl triethoxy silane (MAS) and vinyl triethoxy silane (VS).
  • MAS aminopropyl triethoxy silane
  • VS vinyl triethoxy silane
  • regenerable sorbents based on functionalized POSS-hybrid silica for the removal of C0 2 from a diluted or concentrated gas stream and a method for the preparation of the same is presented.
  • Spray deposition of suitably diluted aged siloxane solution using spray gun produced functionalized POSS based hybrid silica materials capable of C0 2 adsorption in good yield.
  • the C0 2 adsorption is fast and the material can easily be regenerated at low temperatures. These materials can also be regenerated under vacuum or by the combination of temperature and vacuum.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention relève du domaine du développement de sorbants pour l'extraction régénérative de CO2, et concerne plus spécifiquement un POSS (silsesquioxane oligomère polyédrique) fonctionnalisé à base de silice hybride en tant que matériaux sorbants régénérables pour l'extraction du CO2 d'environnements dilués et ultra-dilués. L'invention concerne également un procédé de production associé. L'invention est très utile dans l'extraction régénérative de CO2 de différents environnements tels que des habitats fermés (cabine d'équipage d'engin spatial, sous-marins, etc.) et dans le traitement de gaz effluents industriels.
PCT/IB2016/054474 2015-07-29 2016-07-27 Matériaux de silice hybride à base de poss fonctionnalisé en tant que sorbants régénérables hautement efficaces pour capturer le co2 WO2017017618A1 (fr)

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CN109126749A (zh) * 2018-09-30 2019-01-04 河北大学 一种多面体低聚倍半硅氧烷为壳的核壳型色谱固定相及其制备方法与应用
CN113559828A (zh) * 2021-07-30 2021-10-29 中国农业科学院农业质量标准与检测技术研究所 一种聚丙烯酸磁性纳米复合材料、制备方法及应用
CN114316439A (zh) * 2022-01-12 2022-04-12 青岛颐世保塑料有限公司 畜牧养殖除臭设备用高流动高刚性环保阻燃pp改性料
CN114522667A (zh) * 2022-02-24 2022-05-24 西南科技大学 用于去除放射性碘气体的铋基复合纳米纤维吸附剂的制备及应用
CN114539307A (zh) * 2022-01-05 2022-05-27 苏州仕净科技股份有限公司 一种co2捕集材料、其合成方法以及碳捕集工艺
US11881728B2 (en) 2018-09-07 2024-01-23 Samsung Electronics Co., Ltd Method for confirming state information of wireless charging, and electronic device therefor
CN118126260A (zh) * 2024-05-06 2024-06-04 西南石油大学 一种poss基杂化超临界co2增稠剂及其制备方法

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KOCHUKUNJU ADISSER ET AL: "S-1 Supporting information Functionalized Polysilsesquioxane - Based Hybrid Silica Solid Amine Sorbents for the Regenerative Removal of CO2 from air", ACS APPLIED MATERIALS & INTERFACES, 21 July 2015 (2015-07-21), pages S1 - S11, XP055327670, Retrieved from the Internet <URL:http://pubs.acs.org/doi/suppl/10.1021/acsami.5b04674/suppl_file/am5b04674_si_001.pdf> [retrieved on 20161209] *
KOCHUKUNJU ADISSER SARALADEVI ABHILASH ET AL: "Functionalized Polysilsesquioxane-Based Hybrid Silica Solid Amine Sorbents for the Regenerative Removal of CO 2 from Air", ACS APPLIED MATERIALS AND INTERFACES, vol. 7, no. 32, 21 July 2015 (2015-07-21), US, pages 17969 - 17976, XP055327665, ISSN: 1944-8244, DOI: 10.1021/acsami.5b04674 *

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