WO2023221568A1 - 一种纳米二氧化钛/生物炭复合材料及其制备方法和应用 - Google Patents

一种纳米二氧化钛/生物炭复合材料及其制备方法和应用 Download PDF

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WO2023221568A1
WO2023221568A1 PCT/CN2023/075128 CN2023075128W WO2023221568A1 WO 2023221568 A1 WO2023221568 A1 WO 2023221568A1 CN 2023075128 W CN2023075128 W CN 2023075128W WO 2023221568 A1 WO2023221568 A1 WO 2023221568A1
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biochar
titanium dioxide
preparation
composite material
nano titanium
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PCT/CN2023/075128
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English (en)
French (fr)
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李绍纯
陈旭
胡孟君
刘昂
耿永娟
姜嘉琳
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青岛理工大学
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Priority to US18/280,777 priority Critical patent/US20240174566A1/en
Priority to GB2311816.9A priority patent/GB2625407A/en
Priority to AU2023216735A priority patent/AU2023216735A1/en
Publication of WO2023221568A1 publication Critical patent/WO2023221568A1/zh

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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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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

Definitions

  • the invention relates to the technical field of cement-based materials, and in particular to a nano-titanium dioxide/biochar composite material and its preparation method and application.
  • Nano Titanium dioxide is one of the most widely used 0-dimensional nanomaterials. When it is mixed with cement-based materials, due to its physical filling, self-locking effect, nucleation effect and photocatalytic effect, To a certain extent, it can improve the compressive strength and self-cleaning and other green properties of cement-based materials. However, because NT itself has strong van der Waals forces between molecules and does not participate in the cement hydration reaction, it causes agglomeration, which in turn affects the improvement of the mechanical and durability properties of cement-based materials, and even has negative effects.
  • Biochar is a soil amendment and stable carbon-rich solid. Different from traditional charcoal, which is generally used for fuel, it can be produced through pyrolysis in an airless environment. Contrary to other incineration technologies, Its product releases less carbon dioxide into the atmosphere. At the same time, biochar has adjustable pore structure, functional groups and surface interfacial reactions. Biochar can therefore be used in a variety of environmental applications such as soil remediation, wastewater treatment, chemical recycling and catalyzing biorefinery reactions, as well as carbon capture and storage. It is used in cement materials.
  • the object of the present invention is to provide a nano titanium dioxide/biochar composite material and its preparation Methods and applications: Mixing the nanometer titanium dioxide/biochar composite material of the present invention into cement-based materials can increase the mechanical properties such as compression resistance and flexural strength of the cement-based materials, and at the same time improve the durability of the cement-based materials.
  • the invention provides a preparation method of nano titanium dioxide/biochar composite material, which includes the following steps:
  • the biomass is pyrolyzed, dried and ground in sequence to obtain micron-sized biochar; the pyrolysis temperature is 600 to 750°C;
  • the activated biochar is mixed with dilute sulfuric acid and subjected to electrification to obtain modified biochar;
  • the dispersion and the piperazine solution are mixed to perform a composite reaction to obtain a nano titanium dioxide/biochar composite material; the temperature of the composite reaction is 180°C and the time is 10 to 12 hours.
  • the pyrolysis time is 1 to 2 hours.
  • the surface activation temperature is 60°C
  • the holding time is 2 to 3 hours
  • the concentration of concentrated sulfuric acid is 18 mol/L.
  • the mass ratio of the modified biochar and nano-titanium dioxide is 1:3.
  • the mass ratio of piperazine to nano-titanium dioxide in the piperazine solution is 1:2; the mass fraction of the piperazine solution is 0.05%.
  • the concentration of the dilute sulfuric acid is 10 mol/L; and the time for electrification is 2 to 3 hours.
  • the pH value of the dispersion liquid is adjusted to 12-13.
  • the present invention provides a nanometer titanium dioxide/biochar composite material prepared by the preparation method described in the above solution, including micrometer biochar and nanometer titanium dioxide attached to the surface and pores of the micrometer biochar.
  • the nanometer titanium dioxide/biochar composite material It has a three-dimensional porous structure.
  • the present invention provides the application of the nanometer titanium dioxide/biochar composite material described in the above solution in the preparation of cement-based materials.
  • the cement-based material is exposed to a natural CO 2 environment after standard curing.
  • the invention provides a method for preparing nano titanium dioxide/biochar composite materials, which includes the following steps: pyrolyzing, drying and grinding biomass in sequence to obtain micron-sized biochar; The temperature of the pyrolysis is 600-750°C; the micron-sized biochar is mixed with concentrated sulfuric acid for surface activation to obtain activated biochar; the activated biochar is mixed with dilute sulfuric acid for electrification to obtain modified Biochar; disperse the modified biochar and nano-titanium dioxide into water to obtain a dispersion; mix the dispersion and piperazine solution to perform a composite reaction to obtain a nano-titanium dioxide/biochar composite material; the composite reaction The temperature is 180°C and the time is 10 ⁇ 12h.
  • the present invention introduces nano titanium dioxide into the micron biochar porous structure, which not only improves the high agglomeration problem of nano titanium dioxide, but also reduces the Ca(OH) 2 size and crystal growth through filling, nucleation and other effects in the biochar porous structure. Orientation, resulting in the generation of more CSH gel, filling the pores, improving the interface transition zone (ITZ), and conducive to enhancing mechanical properties such as compressive strength and flexural strength.
  • the nanometer titanium dioxide/biochar composite material of the present invention is incorporated into the cement-based material.
  • the surface layer of the base material improves the absorption capacity of CO 2 through the carbon fixation properties and porous structure of the composite material, and the accelerated hydration characteristics of the nanometer titanium dioxide accelerate the surface layer.
  • Carbonization forms a protective layer of calcium carbonate on the surface, which improves durability; the composite material inside the base material gradually releases water through the porous structure and the water retention and hydrophilicity of the "small size effect" to undergo secondary hydration. Filling pores and refining the internal structure gives cement-based materials excellent mechanical properties and durability.
  • Figure 1 is the XRD pattern of the NT/BC composite material prepared in Example 1;
  • Figure 2 is a graph showing the changes in compressive strength at different ages of the mortar materials prepared by incorporating the NT/BC composite materials of Examples 1 to 4 and the control group;
  • Figure 3 shows the changes in compressive strength at different ages of the mortar materials prepared by incorporating the materials of Comparative Examples 1 to 3 and the control group;
  • Figure 4 is a thermogravimetric analysis diagram of the surface layer of the mortar material prepared by adding the control group
  • Figure 5 is a graph showing the thermogravimetric analysis results of the mortar materials prepared by incorporating the NT/BC composite materials of Examples 1 to 4 and the control group;
  • Figure 6 shows the thermogravimetric analysis results of the mortar materials prepared by incorporating the materials of Comparative Examples 1 to 3 and the control group;
  • Figure 7 shows the carbonized layer that appears after spraying phenolphthalein on the mortar material prepared by incorporating the NT/BC composite material of Example 1;
  • Figure 8 shows the carbonized layer that appears after spraying phenolphthalein on the mortar material prepared from the NT/BC composite material of Examples 1 to 4;
  • Figure 9 is a diagram showing the effects of spraying phenolphthalein on the mortar materials prepared in the control group and Comparative Examples 1 to 3.
  • the invention provides a preparation method of nano titanium dioxide/biochar composite material, which includes the following steps:
  • the biomass is pyrolyzed, dried and ground in sequence to obtain micron-sized biochar; the pyrolysis temperature is 600 to 750°C;
  • the activated biochar is mixed with dilute sulfuric acid and subjected to electrification to obtain modified biochar;
  • the dispersion and the piperazine solution are mixed to perform a composite reaction to obtain a nano titanium dioxide/biochar composite material; the temperature of the composite reaction is 180°C and the time is 10 to 12 hours.
  • biomass is pyrolyzed, dried and ground in sequence to obtain micron-sized biochar.
  • the present invention has no special requirements for the type of biomass, and any biomass well known in the art can be used, such as olivine, sawdust, buckwheat straw, waste wood, animal and plant residues or feces, and hazelnut shells.
  • the biomass is olivine, wood chips or buckwheat straw.
  • the present invention preferably grinds the biomass.
  • the present invention has no special requirements for the grinding process, and a grinding process well known in the art can be used.
  • the pyrolysis is preferably carried out in a pyrolysis reactor.
  • the pyrolysis temperature is 600-750°C, preferably 650-700°C; the pyrolysis time is preferably 1-2h, more preferably 2h.
  • Block biochar easily absorbs water vapor in the air, which affects the modification effect.
  • the present invention dries the block biochar.
  • the drying temperature is preferably 105-120°C, and the heat preservation time is preferably 12 hours.
  • the present invention grinds the obtained biochar.
  • the grinding preferably includes: grinding in an electronically controlled mortar and pestle for 15 minutes, and then grinding for 10 minutes in a turbine sand mill at a speed of 50 Hz and 800 rpm to obtain micron-sized biochar.
  • the The particle size of micron-sized biochar is preferably 100 to 200 ⁇ m.
  • the present invention mixes the micron-sized biochar with concentrated sulfuric acid and performs surface activation to obtain activated biochar.
  • concentration of concentrated sulfuric acid is preferably 18 mol/L.
  • the present invention has no special requirements on the amount of concentrated sulfuric acid, as long as the micron-sized biochar can be completely submerged.
  • the surface activation temperature is preferably 60°C, and the holding time is preferably 2 to 3 hours. The purpose of surface activation of biochar in the present invention is to enhance the adhesion of nano titanium dioxide on the biochar structure.
  • the present invention preferably cools the activation system naturally, then cleans the biochar with absolute ethanol and deionized water in sequence, and obtains activated biochar through centrifugation, filtration, and drying.
  • the present invention mixes the activated biochar with dilute sulfuric acid, conducts electrification, and obtains modified biochar.
  • the concentration of the dilute sulfuric acid is preferably 10 mol/L; the time of the electric polarization is preferably 2 to 3 hours.
  • the present invention has no special requirements on the amount of dilute sulfuric acid, as long as the activated biochar can be submerged.
  • the present invention has no special requirements for the energization conditions, as long as the energization effect is achieved.
  • the present invention utilizes electrification to further activate biochar.
  • the present invention washes the polarized biochar with absolute ethanol and deionized water in sequence, and then centrifuges, filters, and dries to obtain modified biochar.
  • the present invention disperses the modified biochar and nano-titanium dioxide into water to obtain a dispersion liquid.
  • the particle size of the nano-titanium dioxide is preferably 5 to 15 nm; the crystal form of the nano-titanium dioxide is preferably the rutile type.
  • the mass ratio of the modified biochar and nano-titanium dioxide is preferably 1:3.
  • the composite material obtained by controlling the mass ratio of modified biochar and nano-titanium dioxide within the above range has the best performance.
  • the present invention has no special requirements for the dispersion method.
  • the modified biochar and nano-titanium dioxide are directly added to the water and stirred evenly.
  • the water is preferably deionized water.
  • the present invention has no special requirements on the amount of water, as long as the modified biochar and nano-titanium dioxide can be dispersed evenly.
  • the present invention preferably mixes the dispersion liquid and the piperazine solution to perform a composite reaction to obtain a nanometer titanium dioxide/biochar composite material.
  • the present invention preferably adjusts the pH of the dispersion.
  • the value is 12 ⁇ 13.
  • the interior of cement-based materials is an alkaline environment.
  • the present invention adjusts the pH of the dispersion to alkaline, which is beneficial to its application in cement-based materials.
  • the present invention mixes the dispersion liquid and the piperazine solution to perform a composite reaction to obtain nano titanium dioxide/biochar composite material; the temperature of the composite reaction is 180°C and the time is 10 to 12 hours.
  • the mass fraction of the piperazine solution is preferably 0.05%.
  • the mass ratio of piperazine to nano-titanium dioxide in the piperazine solution is preferably 1:2.
  • the function of piperazine is to aminate nano-titanium dioxide, and the aminated nano-titanium dioxide particles increase the attraction and absorption rate of CO 2 .
  • the composite reaction is preferably carried out in a reactor.
  • nanometer titanium dioxide is attached to the biochar.
  • the present invention preferably cools the reaction system, then cleans it with absolute ethanol and deionized water in sequence, and obtains nano titanium dioxide/biochar composite material through centrifugation, filtration, and drying.
  • the present invention provides a nanometer titanium dioxide/biochar composite material prepared by the preparation method described in the above solution, including micrometer biochar and nanometer titanium dioxide attached to the surface and pores of the micrometer biochar.
  • the nanometer titanium dioxide/biochar composite material It has a three-dimensional porous structure.
  • the present invention introduces nano titanium dioxide into the micron biochar porous structure, which not only improves the high agglomeration problem of nano titanium dioxide, but also reduces the Ca(OH) 2 size and crystal growth through filling, nucleation and other effects in the biochar porous structure. Orientation, resulting in the generation of more CSH gel, filling the pores, improving the interface transition zone (ITZ), and conducive to enhancing mechanical properties such as compressive strength and flexural strength.
  • the nanometer titanium dioxide/biochar composite material of the present invention is incorporated into the cement-based material.
  • the surface layer of the base material improves the absorption capacity of CO 2 through the carbon fixation properties and porous structure of the composite material, and the accelerated hydration characteristics of the nanometer titanium dioxide accelerate the surface layer.
  • Carbonization forms a protective layer of calcium carbonate on the surface, which improves durability; the composite material inside the base material gradually releases water through the porous structure and the water retention and hydrophilicity of the "small size effect" to undergo secondary hydration. Filling pores and refining the internal structure gives cement-based materials excellent mechanical properties and durability.
  • the present invention provides the nanometer titanium dioxide/biochar composite material in the preparation of water according to the above scheme.
  • the present invention has no special limitation on the cement-based material. Any cement-based material well known in the art can be used, such as mortar and concrete.
  • the mass content of the nano-titanium dioxide/biochar composite material in the cement-based material is preferably 3 to 5%.
  • the present invention has no special requirements for the preparation process of the cement-based material, and it is sufficient to adopt the preparation process well known in the art.
  • the cement-based material is preferably exposed to a natural CO 2 environment after standard curing.
  • the porous characteristics of the composite material accelerate the absorption of CO 2 in the early stage of hydration, and the nano-titanium dioxide accelerates the hydration of cement to accelerate the carbonization effect.
  • Nano-titanium dioxide/biochar composite The addition of materials enables cement-based materials to exhibit high carbon fixation capabilities and carbonization curing effects in natural CO 2 environments.
  • nano-titanium dioxide/biochar composite material provided by the present invention and its preparation method and application will be described in detail below with reference to the examples, but they should not be understood as limiting the scope of the present invention.
  • NT/BC composite material nano titanium dioxide/biochar composite material
  • Example 1 The only difference from Example 1 is that the olivine is replaced by buckwheat straw.
  • Example 1 The only difference from Example 1 is that the olivine is replaced with wood chips.
  • Example 1 The only difference from Example 1 is that the pyrolysis temperature is 600°C.
  • the obtained massive porous biochar was dried in an oven at 120°C for 12 hours, then ground in an electronically controlled mortar and pestle for 15 minutes, and then ground in a turbine sand mill at 50 Hz and 800 rpm for 10 minutes to obtain micron-sized biochar. bio-charcoal.
  • Example 1 The only difference from Example 1 is that steps (3) and (4) were not performed, that is, the biochar was not modified. The rest was the same as in Example 1, and an NT/BC composite material prepared from unmodified biochar was obtained.
  • the NT/BC composite material prepared in Example 1 was characterized by The composite effect of titanium dioxide and biochar is better.
  • the control group in Table 1 is normal cement mortar without other materials.
  • the test plan is as follows:
  • thermogravimetric analysis TGA of the sample surface layer measured 24 hours after the control group was removed from the mold in a natural CO2 exposure environment is shown in Figure 4.
  • the content changes of Ca(OH) 2 and CaCO 3 can be obtained through thermogravimetric analysis.
  • thermogravimetric analysis results of the surface layer of the sample measured 24 hours after removal of the formwork of the mortar material prepared by adding the materials of each example and comparative example in a natural CO 2 exposure environment are shown in Figures 5 and 6, and the corresponding data are shown in Table 1. It can be seen from the results of Figure 5, Figure 6 and Table 1 that compared with single-doped nano titanium dioxide or biochar, the addition of NT/BC composite materials in Examples 1 to 4 increased the CaCO 3 content, indicating that there is an improvement in carbon absorption. has seen an increase.
  • Figures 7 to 9 show the effects of the control group and the mortar materials obtained by mixing the materials of Examples 1 to 4 and Comparative Examples 1 to 3 after spraying with phenolphthalein.
  • Figure 7 shows the carbonized layer that appears after the mortar material prepared by incorporating the NT/BC composite material of Example 1 is sprayed with phenolphthalein
  • Figure 8 shows the carbonized layer that appears after the mortar material prepared by the NT/BC composite material of Examples 1 to 4 is sprayed with phenolphthalein.
  • the carbonized layer from left to right, is Example 2, Example 4, Example 1 and Example 3;
  • Figure 9 shows the effect of the control group and the mortar materials prepared in Comparative Examples 1 to 3 after spraying phenolphthalein, from left To the right are the control group, Comparative Example 1, Comparative Example 2 and Comparative Example 3.
  • Microscopic tests show that a dense carbonized layer is formed on the surface of the sample prepared by incorporating the NT/BC composite material of Examples 1 to 4 (as shown in Figure 7), which prevents the carbonization from continuing to deepen.
  • Example 2 When the mortar material prepared by incorporating the materials of Example 2 was exposed to natural CO2 , it was measured that the CH content of the surface layer of the sample 24 hours after the mold was removed did not decrease significantly, because buckwheat straw, as a silicon-based biomass, has a certain degree of volcanic ash effect. In addition, it was also observed through microscopic inspection that a dense carbonized layer was formed on the surface layer, and the carbonization depth was inferior to that in Example 1. There is no carbonization layer formed on the surface of the sample doped with nanometer titanium dioxide or biochar alone, the carbonization depth is higher, and the internal structure is less dense, which is reflected in the macroscopic mechanical properties. The addition of NT/BC composites made from unmodified biochar increased carbon absorption compared with the unmodified biochar, but did not form dense carbonization on the surface. layer, and the carbonization depth is relatively high.

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Abstract

本发明提供了一种纳米二氧化钛/生物炭复合材料及其制备方法和应用，属于水泥基材料技术领域。本发明将纳米二氧化钛引入微米生物炭多孔结构中，既改善了纳米二氧化钛的高团聚问题，且纳米二氧化钛在生物炭多孔结构中通过填充、成核等效应，降低Ca(OH)2尺寸和晶体生长取向，使得生成更多的C-S-H凝胶，填充了孔隙，改善了界面过渡区(ITZ)，又有利于增强抗压、抗弯强度等力学性能。将本发明的纳米二氧化钛/生物炭复合材料内掺入水泥基材料内，基材表层通过复合材料固碳特性和多孔结构提高对CO2的吸收能力，以及纳米二氧化钛的加速水化特性加速了表层碳化作用，形成表面碳酸钙保护层，提高了耐久性能。

Description

一种纳米二氧化钛/生物炭复合材料及其制备方法和应用
本申请要求于2022年05月20日提交中国专利局、申请号为CN202210558730.8、发明名称为“一种纳米二氧化钛/生物炭复合材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及水泥基材料技术领域，尤其涉及一种纳米二氧化钛/生物炭复合材料及其制备方法和应用。
背景技术
纳米二氧化钛(Nano Titanium dioxide，NT)是一种应用最广泛的0维纳米材料之一，当其内掺入水泥基材料后，由于其物理填充、自锁效应和成核效应以及光催化效应，一定程度上可以提高水泥基材料的抗压强度和自清洁等绿色性能。但是因为NT本身存在分子间较强的范德华力，且不参与水泥水化反应等特点，这导致其存在团聚现象，进而影响对水泥基材料的力学及耐久性能提升作用，甚至出现负面效果。
生物炭(Biochar,BC)是一种作为土壤改良剂和稳定的富碳固体，有别于一般用于燃料的传统木炭，其可在无空气环境下通过热解产生，与其他焚烧技术相反，其产物进入大气的二氧化碳较少。同时，生物炭具有可调节的孔隙结构、官能团和表面的界面反应。因此，生物炭可用于各种环境应用，如土壤修复、废水处理、化学回收和催化生物精炼反应，以及碳捕集和储存。其应用于水泥材料中，通过其多孔结构特性和硅基生物炭的“火山灰效应”会影响水泥水化过程中钙矾石、C-S-H凝胶等水化产物的晶形生长方式；此外，其固碳特性在水泥基材料碳吸收和利用上具有广阔前景。然而，由于生物炭自身的脆性和多孔性等因素使得水泥材料抗压、抗弯和抗折强度产生消极影响。
发明内容
本发明的目的在于提供一种纳米二氧化钛/生物炭复合材料及其制备 方法和应用，将本发明的纳米二氧化钛/生物炭复合材料内掺到水泥基材料中，可以增加水泥基材料的抗压、抗弯强度等力学性能，同时提升水泥基材料的耐久性。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种纳米二氧化钛/生物炭复合材料的制备方法，包括以下步骤：
将生物质依次进行热解、干燥和研磨，得到微米级生物炭；所述热解的温度为600～750℃；
将所述微米级生物炭与浓硫酸混合，进行表面活化，得到活化生物炭；
将所述活化生物炭与稀硫酸混合，进行通电极化，得到改性生物炭；
将所述改性生物炭和纳米二氧化钛分散到水中，得到分散液；
将所述分散液和哌嗪溶液混合，进行复合反应，得到纳米二氧化钛/生物炭复合材料；所述复合反应的温度为180℃，时间为10～12h。
优选的，所述热解的时间为1～2h。
优选的，所述表面活化的温度为60℃，保温时间为2～3h；所述浓硫酸的浓度为18mol/L。
优选的，所述改性生物炭和纳米二氧化钛的质量比为1:3。
优选的，所述哌嗪溶液中哌嗪与纳米二氧化钛的质量比为1:2；所述哌嗪溶液的质量分数为0.05％。
优选的，所述稀硫酸的浓度为10mol/L；所述通电极化的时间为2～3h。
优选的，将所述分散液和哌嗪溶液混合前，还包括调整所述分散液的pH值为12～13。
本发明提供了上述方案所述制备方法制备得到的纳米二氧化钛/生物炭复合材料，包括微米生物炭和附着于所述微米生物炭表面和孔道中的纳米二氧化钛，所述纳米二氧化钛/生物炭复合材料具有三维多孔结构。
本发明提供了上述方案所述纳米二氧化钛/生物炭复合材料在制备水泥基材料中的应用。
优选的，所述水泥基材料经标准养护后置于自然CO2环境中暴露。
本发明提供了一种纳米二氧化钛/生物炭复合材料的制备方法，包括以下步骤：将生物质依次进行热解、干燥和研磨，得到微米级生物炭；所 述热解的温度为600～750℃；将所述微米级生物炭与浓硫酸混合，进行表面活化，得到活化生物炭；将所述活化生物炭与稀硫酸混合，进行通电极化，得到改性生物炭；将所述改性生物炭和纳米二氧化钛分散到水中，得到分散液；将所述分散液和哌嗪溶液混合，进行复合反应，得到纳米二氧化钛/生物炭复合材料；所述复合反应的温度为180℃，时间为10～12h。
本发明将纳米二氧化钛引入微米生物炭多孔结构中，既改善了纳米二氧化钛的高团聚问题，且纳米二氧化钛在生物炭多孔结构中通过填充、成核等效应，降低Ca(OH)2尺寸和晶体生长取向，使得生成更多的C-S-H凝胶，填充了孔隙，改善了界面过渡区(ITZ)，又有利于增强抗压、抗弯强度等力学性能。
将本发明的纳米二氧化钛/生物炭复合材料内掺入水泥基材料内，基材表层通过复合材料固碳特性和多孔结构提高对CO2的吸收能力，以及纳米二氧化钛的加速水化特性加速了表层碳化作用，形成表面碳酸钙保护层，提高了耐久性能；在基材内部的复合材料通过多孔结构与“小尺寸效应”的保水性和亲水性对水分的逐渐释放发生二次水化作用，填充孔隙，细化内部结构，使得水泥基材料具有优异的力学性能和耐久性。
说明书附图
图1为实施例1制备的NT/BC复合材料的XRD图；
图2为掺入实施例1～4的NT/BC复合材料制备的砂浆材料及对照组不同龄期的抗压强度变化图；
图3为掺入对比例1～3材料制备的砂浆材料及对照组不同龄期的抗压强度变化图；
图4为掺入对照组制备的砂浆材料的表层热重分析图；
图5为掺入实施例1～4的NT/BC复合材料制备的砂浆材料及对照组的热重分析结果图；
图6为掺入对比例1～3材料制备的砂浆材料及对照组的热重分析结果图；
图7为掺入实施例1的NT/BC复合材料制备的砂浆材料喷涂酚酞后显现的碳化层；
图8为实施例1～4的NT/BC复合材料制备的砂浆材料喷涂酚酞后显现的碳化层；
图9为对照组和对比例1～3制备的砂浆材料喷涂酚酞后显现效果图。
具体实施方式
下面结合实施例和附图对本发明进一步说明。
本发明提供了一种纳米二氧化钛/生物炭复合材料的制备方法，包括以下步骤：
将生物质依次进行热解、干燥和研磨，得到微米级生物炭；所述热解的温度为600～750℃；
将所述微米级生物炭与浓硫酸混合，进行表面活化，得到活化生物炭；
将所述活化生物炭与稀硫酸混合，进行通电极化，得到改性生物炭；
将所述改性生物炭和纳米二氧化钛分散到水中，得到分散液；
将所述分散液和哌嗪溶液混合，进行复合反应，得到纳米二氧化钛/生物炭复合材料；所述复合反应的温度为180℃，时间为10～12h。
在本发明中，未经特殊说明，所用原料均为本领域熟知的市售商品。
本发明将生物质依次进行热解、干燥和研磨，得到微米级生物炭。
本发明对所述生物质的种类没有特殊要求，本领域熟知的生物质均可，具体的如橄榄石、木屑、荞麦秆、废旧木材、动植物残渣或粪便、榛子壳。在本发明的实施例中，所述生物质为橄榄石、木屑或荞麦秆。
所述热解前，本发明优选将生物质进行磨碎。本发明对所述磨碎的过程没有特殊要求，采用本领域熟知的磨碎过程即可。在本发明中，所述热解优选在热解反应器中进行。在本发明中，所述热解的温度为600～750℃，优选为650～700℃；所述热解的时间优选为1～2h，更优选为2h。
热解后，本发明得到块状生物炭。块状生物炭易吸收空气中的水蒸气，影响改性效果，本发明对所述块状生物炭进行干燥。
在本发明中，所述干燥的温度优选为105～120℃，保温时间优选为12h。完成所述干燥后，本发明将所得生物炭进行研磨。在本发明中，所述研磨优选包括：在电控研钵杵中研磨15min，之后在涡轮砂磨机50Hz、800转/分的转速下研磨10min，制得微米级生物炭。在本发明中，所述 微米级生物炭的粒径优选为100～200μm。
得到微米级生物炭后，本发明将所述微米级生物炭与浓硫酸混合，进行表面活化，得到活化生物炭。在本发明中，所述浓硫酸的浓度优选为18mol/L。本发明对所述浓硫酸的用量没有特殊要求，能够将微米级生物炭完全浸没即可。在本发明中，所述表面活化的温度优选为60℃，保温时间优选为2～3h。本发明对生物炭进行表面活化的目的是增强纳米二氧化钛在生物炭结构上的附着。
完成所述表面活化后，本发明优选将活化体系自然冷却，然后用无水乙醇和去离子水依次清洗生物炭，经离心、过滤、干燥，得到活化生物炭。
得到活化生物炭后，本发明将所述活化生物炭与稀硫酸混合，进行通电极化，得到改性生物炭。
在本发明中，所述稀硫酸的浓度优选为10mol/L；所述通电极化的时间优选为2～3h。本发明对所述稀硫酸的用量没有特殊要求，能将活化生物炭没过即可。本发明对所述通电的条件没有特殊要求，达到通电效果即可。本发明利用通电极化进一步活化生物炭。
完成所述通电极化后，本发明将极化后的生物炭依次用无水乙醇和去离子水清洗，经离心、过滤、干燥，得到改性生物炭。
得到改性生物炭后，本发明将所述改性生物炭和纳米二氧化钛分散到水中，得到分散液。
在本发明中，所述纳米二氧化钛的粒径优选为5～15nm；所述纳米二氧化钛的晶型优选为金红石型。在本发明中，所述改性生物炭和纳米二氧化钛的质量比优选为1:3。本发明将改性生物炭和纳米二氧化钛的质量比控制在上述范围得到的复合材料的性能最好。
本发明对所述分散的方式没有特殊要求，在本发明的实施例中直接将改性生物炭和纳米二氧化钛加入到水中，搅拌均匀即可。在本发明中，所述水优选为去离子水。本发明对所述水的用量没有特殊要求，能够将改性生物炭和纳米二氧化钛分散均匀即可。
得到分散液后，本发明优选将所述分散液和哌嗪溶液混合，进行复合反应，得到纳米二氧化钛/生物炭复合材料。
将所述分散液和哌嗪溶液混合前，本发明优选调整所述分散液的pH 值为12～13。水泥基材料内部为碱性环境，本发明将分散液调节pH至碱性有利于在水泥基材料中的应用。本发明优选采用0.02mol/L NaNO3和2mol/L NaOH的混合溶液调整pH。
得到分散液后，本发明将所述分散液和哌嗪溶液混合，进行复合反应，得到纳米二氧化钛/生物炭复合材料；所述复合反应的温度为180℃，时间为10～12h。
在本发明中，所述哌嗪溶液的质量分数优选为0.05％。在本发明中，所述哌嗪溶液中哌嗪与纳米二氧化钛的质量比优选为1:2。在本发明中，哌嗪的作用是对纳米二氧化钛进行胺化，胺化后的纳米二氧化钛颗粒增加了对CO2的吸引力和吸收率。
在本发明中，所述复合反应优选在反应釜中进行。本发明在所述复合反应过程中，纳米二氧化钛附着到生物炭上。
完成所述复合反应后，本发明优选将反应体系冷却，然后依次用无水乙醇和去离子水清洗，经离心、过滤、干燥，得到纳米二氧化钛/生物炭复合材料。
本发明提供了上述方案所述制备方法制备得到的纳米二氧化钛/生物炭复合材料，包括微米生物炭和附着于所述微米生物炭表面和孔道中的纳米二氧化钛，所述纳米二氧化钛/生物炭复合材料具有三维多孔结构。
本发明将纳米二氧化钛引入微米生物炭多孔结构中，既改善了纳米二氧化钛的高团聚问题，且纳米二氧化钛在生物炭多孔结构中通过填充、成核等效应，降低Ca(OH)2尺寸和晶体生长取向，使得生成更多的C-S-H凝胶，填充了孔隙，改善了界面过渡区(ITZ)，又有利于增强抗压、抗弯强度等力学性能。
将本发明的纳米二氧化钛/生物炭复合材料内掺入水泥基材料内，基材表层通过复合材料固碳特性和多孔结构提高对CO2的吸收能力，以及纳米二氧化钛的加速水化特性加速了表层碳化作用，形成表面碳酸钙保护层，提高了耐久性能；在基材内部的复合材料通过多孔结构与“小尺寸效应”的保水性和亲水性对水分的逐渐释放发生二次水化作用，填充孔隙，细化内部结构，使得水泥基材料具有优异的力学性能和耐久性。
本发明提供了上述方案所述纳米二氧化钛/生物炭复合材料在制备水 泥基材料中的应用。本发明对所述水泥基材料没有特殊的限定，本领域熟知的水泥基材料均可，具体的如：砂浆、混凝土。在本发明中，所述纳米二氧化钛/生物炭复合材料在水泥基材料中的质量掺量优选为3～5％。
本发明对所述水泥基材料的制备过程没有特殊要求，采用本领域熟知的制备过程即可。在本发明中，所述水泥基材料经标准养护后优选置于自然CO2环境中暴露。
现有技术大多仅限于单掺不同含量的纳米二氧化钛或者生物炭，在碳吸收方面，两者单掺型均应用于营造高浓度CO2环境进行碳化养护以促进大气中碳吸收，然而营造这一高浓度CO2环境存在成本等一系列问题。本发明不仅做到了抗压、抗弯等力学、耐久性能的双向同步提升外，还避免了创造高浓度CO2环境带来的成本等问题，一方面，生物炭本身具有固碳特性，对CO2具有较强吸引力，另一方面，复合材料的多孔特性使得在水化早期加速了CO2的吸收，以及纳米二氧化钛的加速水泥水化等作用来加速了碳化效果，纳米二氧化钛/生物炭复合材料的加入使得水泥基材料在自然CO2环境下即能表现出高固碳能力和碳化养护效果。
下面结合实施例对本发明提供的纳米二氧化钛/生物炭复合材料及其制备方法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
(1)将橄榄石磨碎置于热解反应器中，在700℃下热解2h，制得块状生物炭；
(2)将制得的块状多孔生物炭在烘箱中120℃干燥12h，然后在电控研钵杵中研磨15min，之后在涡轮砂磨机50Hz、800转/分的转速下研磨10min，制得微米级生物炭；
(3)取微米级生物炭混合浓H2SO4(18mol/L)，在60℃加热2h进行表面活化，自然冷却后用无水乙醇和去离子水依次清洗，经离心、过滤、干燥，得到活化生物炭；
(4)将活化生物炭在10mol/L的H2SO4溶液中通电极化2h，依次用无水乙醇和去离子水清洗，经离心、过滤、干燥，得到改性生物炭；
(5)取质量比为1：3的改性生物炭和纳米二氧化钛(市场所购买的金红石型，粒径为5nm～15nm，亲水性)同时加入含50mL去离子水的烧杯中混合均匀，搅拌过程中使用0.02mol/L NaNO3和2mol/L NaOH的混合溶液调节pH值为12.5±0.5，将混合溶液与质量分数为0.05％哌嗪(PZ)溶液倒入反应釜中，哌嗪与纳米二氧化钛质量比为1：2，在烘箱中180℃加热12h进行复合反应；
(6)待混合溶液冷却后，依次用无水乙醇和去离子水清洗，经离心、过滤、干燥，得到纳米二氧化钛/生物炭复合材料，简写为NT/BC复合材料。
实施例2
与实施例1的不同之处仅在于将橄榄石替换为荞麦秆。
实施例3
与实施例1的不同之处仅在于将橄榄石替换为木屑。
实施例4
与实施例1的不同之处仅在于热解的温度为600℃。
对比例1
纳米二氧化钛。
对比例2
将橄榄石磨碎置于热解反应器中，在700℃下热解2h，制得块状生物炭；
将制得的块状多孔生物炭在烘箱中120℃干燥12h，然后在电控研钵杵中研磨15min，之后在涡轮砂磨机50Hz、800转/分的转速下研磨10min，制得微米级生物炭。
对比例3
与实施例1的区别仅在于未进行步骤(3)和(4)，即未对生物炭进行改性，其余同实施例1，得到未改性的生物炭制备的NT/BC复合材料。
性能表征:
1、对实施例1制备的NT/BC复合材料进行XRD表征，结果如图1所示，由图1可知，制备的NT/BC复合材料中同时存在纳米二氧化钛与生物炭的特征峰，表明纳米二氧化钛与生物炭复合效果较好。
2、将各实施例制备的NT/BC复合材料、纳米二氧化钛(对比例1)、生物炭(对比例2)和未改性的生物炭制备的NT/BC复合材料(对比例3)分别应用于水泥砂浆(水胶比w/b＝0.35)中，检测其性能影响，具体步骤如下：
分别称取18gNT/BC复合材料(mNT：mBC＝3：1)、纳米二氧化钛、生物炭、未改性的生物炭制备的NT/BC复合材料与135mL水置于搅拌锅中混合搅拌15s，加入450g水泥(P.O 42.5)开启砂浆搅拌机快速搅拌30s后，在低速30s搅拌过程中加入1350g标准砂，依次进行30s快速搅拌、60s静置手动搅拌、60s快速搅拌，制得新拌砂浆进行浇筑成模。经过24h标准养护(20±2℃，湿度＞95％)后拆模，测得3d、28d龄期的抗压强度如图2和图3所示。对应的结果见表1。注：采用标准水泥砂浆搅拌机进行搅拌，快速与低速速率是恒定的。
表1中对照组为未掺入其他材料的正常水泥砂浆，试验方案如下：
称取135mL水置于搅拌锅中，加入450g水泥(P.O 42.5)开启砂浆搅拌机快速搅拌30s后，在低速30s搅拌过程中加入1350g标准砂，依次进行30s快速搅拌、60s静置手动搅拌、60s快速搅拌，制得新拌普通水泥砂浆进行浇筑成模。经过24h标准养护后拆模，测得3d、28d龄期的抗压强度如图2和图3所示，对应的结果见表1。
表1实施例和对比例的抗压强度、氢氧化钙(CH)含量和CaCO3含量

由表1的结果可知，相比对照组，实施例1～4制备的NT/BC复合材料的加入对3d、28d龄期的抗压强度提升显著，同时对抗弯强度也起到明显的提高。在抗压、抗弯强度提高上，NT/BC复合材料性能均显著优于NT和BC单独加入，改性后的生物炭制备的NT/BC复合材料性能优于未改性的生物炭制备的NT/BC复合材料。
此外，在经过自然CO2暴露环境下，测得对照组拆模后24h的试样表层热重分析(TGA)如图4所示。通过热重分析可以得到Ca(OH)2和CaCO3的含量变化。
添加各实施例和对比例材料制备的砂浆材料在经过自然CO2暴露环境下，测得拆模后24h的试样表层热重分析结果见图5和图6，对应的数据见表1。由图5、图6和表1的结果可知，与单掺纳米二氧化钛或生物炭相比而言，实施例1～4中NT/BC复合材料的加入使得CaCO3含量增加，说明在碳吸收上有所提高。
对照组、掺入实施例1～4和对比例1～3材料得到的砂浆材料喷涂酚酞后显现效果如图7～9所示。其中，图7为掺入实施例1的NT/BC复合材料制备的砂浆材料喷涂酚酞后显现的碳化层；图8为实施例1～4的NT/BC复合材料制备的砂浆材料喷涂酚酞后显现的碳化层，从左至右依次为实施例2、实施例4、实施例1和实施例3；图9为对照组和对比例1～3制备的砂浆材料喷涂酚酞后显现效果图，从左至右依次为对照组、对比例1、对比例2和对比例3。微观测试表明，掺入实施例1～4的NT/BC复合材料制备的试样的表面形成致密的碳化层(如图7所示)，阻止了碳化的持续深入。掺入实施例2材料制备的砂浆材料经过自然CO2暴露环境下，测得拆模后24h的试样表层CH含量降低不明显，因为荞麦秆作为硅基生物质而具备一定程度的火山灰效应，此外通过微观检测也观察到表层形成了致密的碳化层，碳化深度次于实施例1。单掺纳米二氧化钛或生物炭的试样表面未形成碳化层且碳化深度更高，内部结构致密程度较差，在宏观力学性能上得以体现。未改性的生物炭制得的NT/BC复合材料的加入相比未掺加时在碳吸收上有所增加，但在表面未形成致密的碳化 层，且碳化深度较高。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (14)

  1. 一种纳米二氧化钛/生物炭复合材料的制备方法，其特征在于，包括以下步骤：
    将生物质依次进行热解、干燥和研磨，得到微米级生物炭；所述热解的温度为600～750℃；
    将所述微米级生物炭与浓硫酸混合，进行表面活化，得到活化生物炭；
    将所述活化生物炭与稀硫酸混合，进行通电极化，得到改性生物炭；
    将所述改性生物炭和纳米二氧化钛分散到水中，得到分散液；
    将所述分散液和哌嗪溶液混合，进行复合反应，得到纳米二氧化钛/生物炭复合材料；所述复合反应的温度为180℃，时间为10～12h。
  2. 根据权利要求1所述的制备方法，其特征在于，所述热解的时间为1～2h。
  3. 根据权利要求1所述的制备方法，其特征在于，所述表面活化的温度为60℃，保温时间为2～3h；所述浓硫酸的浓度为18mol/L。
  4. 根据权利要求1所述的制备方法，其特征在于，所述改性生物炭和纳米二氧化钛的质量比为1:3。
  5. 根据权利要求1所述的制备方法，其特征在于，所述哌嗪溶液中哌嗪与纳米二氧化钛的质量比为1:2；所述哌嗪溶液的质量分数为0.05％。
  6. 根据权利要求1所述的制备方法，其特征在于，所述稀硫酸的浓度为10mol/L；所述通电极化的时间为2～3h。
  7. 根据权利要求1所述的制备方法，其特征在于，将所述分散液和哌嗪溶液混合前，还包括调整所述分散液的pH值为12～13。
  8. 根据权利要求1所述的制备方法，其特征在于，所述微米级生物炭的粒径为100～200μm。
  9. 根据权利要求1所述的制备方法，其特征在于，所述纳米二氧化钛的粒径为5～15nm。
  10. 根据权利要求1或9所述的制备方法，其特征在于，所述纳米二氧化钛的晶型为金红石型。
  11. 权利要求1～10任一项所述制备方法制备得到的纳米二氧化钛/ 生物炭复合材料，包括微米生物炭和附着于所述微米生物炭表面和孔道中的纳米二氧化钛，所述纳米二氧化钛/生物炭复合材料具有三维多孔结构。
  12. 权利要求11所述纳米二氧化钛/生物炭复合材料在制备水泥基材料中的应用。
  13. 根据权利要求12所述的应用，其特征在于，所述水泥基材料经标准养护后置于自然CO2环境中暴露。
  14. 根据权利要求12或13所述的应用，其特征在于，所述纳米二氧化钛/生物炭复合材料在水泥基材料中的质量掺量为3～5％。
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