CN111514854A - Preparation method of modified 3D porous carbon composite adsorption material - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 24
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 51
- 239000003463 adsorbent Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 159000000009 barium salts Chemical class 0.000 claims abstract description 3
- 150000001621 bismuth Chemical class 0.000 claims abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 12
- 150000001721 carbon Chemical class 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000012876 carrier material Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 159000000001 potassium salts Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 5
- 241001330002 Bambuseae Species 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013401 experimental design Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract
一种改性3D多孔碳复合吸附材料的制备方法，涉及复合改性制备活性炭吸附材料技术领域，首先将钾盐、钡盐、铋盐溶于水中混合均匀，再加入活性炭并混合均匀，然后通过超声波微波组合反应器进行反应，制备获得改性3D多孔碳复合吸附材料。本发明以3D多孔碳为主要载体物质，以一定含量和组成的K2O‑Bi2O3‑BaO为吸附材料的填充剂，以最新发展的超声微波组合法制备性能优良的复合吸附材料。同时，采用不同摩尔比掺杂K2O‑Bi2O3‑BaO物质离子对多孔碳吸附材料进行改性研究。获得了较佳的复合3D多孔碳组分吸附剂材料。不同组成的系列多孔碳复合材料对含Pb(Ⅱ)离子重金属离子溶液吸附量与去除时间、物质组成均不同。
A method for preparing a modified 3D porous carbon composite adsorption material relates to the technical field of composite modified activated carbon adsorption materials. First, potassium salts, barium salts and bismuth salts are dissolved in water and mixed uniformly, and then activated carbon is added and mixed uniformly. The modified 3D porous carbon composite adsorption material is prepared by reacting in an ultrasonic microwave combined reactor. The invention uses 3D porous carbon as the main carrier material, uses K 2 O-Bi 2 O 3 -BaO with a certain content and composition as the filler of the adsorption material, and prepares the composite adsorption material with excellent performance by the newly developed ultrasonic-microwave combination method. At the same time, the porous carbon adsorbents were modified by doping K 2 O‑Bi 2 O 3 -BaO with different molar ratios. A better composite 3D porous carbon component adsorbent material was obtained. A series of porous carbon composites with different compositions have different adsorption capacity, removal time and material composition for heavy metal ion solution containing Pb(Ⅱ) ions.
Description
技术领域technical field
本发明涉及复合改性制备活性炭吸附材料技术领域，具体是涉及一种改性3D多孔碳复合吸附材料的制备方法。The invention relates to the technical field of composite modified preparation of activated carbon adsorption materials, in particular to a preparation method of a modified 3D porous carbon composite adsorption material.
背景技术Background technique
近年来，随着经济和科学技术的飞速发展，多孔碳材料是一种无污染、无害环境的吸附剂材料。大量的实验和研究表明，复合多孔碳材料由于其独特的性能，比单一多孔碳材料具有更好的吸附和催化性能。多孔碳复合吸附材料由于其具有丰富的孔状结构、超高比表面积，丰富的表面官能团，在吸附分离、污水处理、气体净化等领域广泛应用。In recent years, with the rapid development of economy and science and technology, porous carbon material is a non-polluting and environmentally friendly adsorbent material. Numerous experiments and studies have shown that composite porous carbon materials have better adsorption and catalytic properties than single porous carbon materials due to their unique properties. Porous carbon composite adsorption materials are widely used in adsorption separation, sewage treatment, gas purification and other fields due to their rich pore structure, ultra-high specific surface area, and rich surface functional groups.
3D多孔碳材料因其独特的三维结构目前被广泛关注，它具有独特的骨架结构、较高的表面积、定向的孔道分布，具有较高的化学稳定性，表现出较强的双电层效应，还能够负载一定量的金属化合物，作为锂电、锂硫、超级电容器的碳电极材料。3D porous carbon materials have been widely concerned because of their unique three-dimensional structure. It can also support a certain amount of metal compounds as carbon electrode materials for lithium batteries, lithium sulfur, and supercapacitors.
3D多孔碳材料常见的合成方法有碳化法、物理化学活化法、催化活化法、有机凝胶碳化法、自组装法和模板法等。催化活化法金属易进入并滞留在多孔碳内部，有机凝胶碳化法设备昂贵制备过程较繁琐，且有机气凝胶的前驱体使用酚、醛类等有毒性的有机物，对工作人员和环境有一定的危险性。传统模板法的模板合成过程较为繁琐、成本较为高昂等，都限制了其在工业生产的大规模应用。Common synthetic methods of 3D porous carbon materials include carbonization, physicochemical activation, catalytic activation, organogel carbonization, self-assembly, and template methods. The catalytic activation method metal is easy to enter and stay in the porous carbon, the organogel carbonization method is expensive and the preparation process is cumbersome, and the organic aerogel precursors use toxic organics such as phenols and aldehydes, which are harmful to workers and the environment. certain risk. The template synthesis process of the traditional template method is cumbersome and the cost is relatively high, which limits its large-scale application in industrial production.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是提出一种改性3D多孔碳复合吸附材料的制备方法，以制备可以用于含铅离子的工业污水废水环境治理的吸附材料。The technical problem to be solved by the present invention is to propose a preparation method of a modified 3D porous carbon composite adsorption material, so as to prepare an adsorption material that can be used for environmental treatment of industrial sewage wastewater containing lead ions.
为了实现上述目的，本发明所采用的技术方案为：一种改性3D多孔碳复合吸附材料的制备方法，首先将钾盐、钡盐、铋盐溶于水中混合均匀，再加入活性炭并混合均匀，然后通过超声波微波组合反应器进行反应，制备获得改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO。In order to achieve the above purpose, the technical scheme adopted in the present invention is as follows: a preparation method of a modified 3D porous carbon composite adsorption material, firstly, potassium salt, barium salt and bismuth salt are dissolved in water and mixed uniformly, then activated carbon is added and mixed uniformly , and then reacted in an ultrasonic microwave combined reactor to prepare a modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO.
作为本发明的改性3D多孔碳复合吸附材料的制备方法的优选技术方案，具体步骤如下：As a preferred technical solution for the preparation method of the modified 3D porous carbon composite adsorption material of the present invention, the specific steps are as follows:
1)、称取硝酸钾、硝酸钡、硝酸铋加入烧杯中，使用蒸馏水溶解，磁力搅拌下加入氨水调节溶液的pH值至9-12，充分搅拌后，用氨水溶液调其pH；1), take potassium nitrate, barium nitrate, bismuth nitrate and add in the beaker, use distilled water to dissolve, add the pH value of ammonia solution to 9-12 under magnetic stirring, after fully stirring, adjust its pH with ammonia solution;
2)、将活性炭粉球磨均匀颗粒至1～5μm的细粉，然后加入至溶液中，充分搅拌后，再次用氨水溶液调其pH至9-12；2), ball mill the activated carbon powder to a fine powder of 1-5 μm, then add it to the solution, after fully stirring, adjust its pH to 9-12 with ammonia solution again;
3)、将溶液置于超声波微波组合反应器中进行反应，采用超声波1200W+微波1000W双功能化反应30min；3), place the solution in the ultrasonic microwave combined reactor to react, and adopt ultrasonic 1200W+microwave 1000W bifunctional reaction for 30min;
4)、反应结束后，将样品放入150℃烘箱中干燥6h，获得改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO。4) After the reaction, put the sample into a 150° C. oven to dry for 6 hours to obtain a modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO.
作为本发明的改性3D多孔碳复合吸附材料的制备方法的进一步优选技术方案，所述活性炭选自煤质活性炭粉、竹木活性炭粉、椰壳活性炭粉中的一种。改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO中C、K2O、Bi2O3和BaO的掺杂摩尔比为5～10：1～5：1～5：1～5。进一步优选地，改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO中C、K2O、Bi2O3和BaO的掺杂摩尔比为7：1：2：1。As a further preferred technical solution of the preparation method of the modified 3D porous carbon composite adsorption material of the present invention, the activated carbon is selected from one of coal-based activated carbon powder, bamboo and wood activated carbon powder, and coconut shell activated carbon powder. The doping molar ratio of C, K 2 O, Bi 2 O 3 and BaO in the modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO is 5-10:1-5:1-5:1 ~5. Further preferably, the doping molar ratio of C, K 2 O, Bi 2 O 3 and BaO in the modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO is 7:1:2:1.
本发明提出了一种改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO，微观形态呈由片形、棒状、四面体状等形状而组成的多孔结构，复合材料的微结构尺寸范围在500nm-2um之间。The invention proposes a modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO, whose microscopic morphology is a porous structure composed of a sheet shape, a rod shape, a tetrahedron shape, etc. The microstructure of the composite material is The size range is between 500nm-2um.
与现有技术相比，本发明的有益效果表现在：Compared with the prior art, the beneficial effects of the present invention are shown in:
本发明以制备的3D多孔碳为主要载体物质，以一定含量和组成的K2O-Bi2O3-BaO为吸附材料的填充剂，以最新发展的超声微波组合法制备性能优良的复合吸附材料。同时，采用不同摩尔比掺杂K2O-Bi2O3-BaO物质离子对多孔碳吸附材料进行改性研究。用XRD、SEM等手段对改性后的多孔碳复合吸附材料进行了表征。通过微结构和组分比较，选择了较好的系列改性多孔碳复合吸附材料，并对其吸附性能进行了研究和分析，获得了较佳的复合3D多孔碳组分吸附剂材料。实验发现，不同组成的系列多孔碳复合材料对含Pb(Ⅱ)离子重金属离子溶液吸附量与去除时间、物质组成均不同。结果发现，K2O-Bi2O3-BaO(1：2：1)改性3D多孔碳(70％)吸附效果最好，吸附量达到239mg/g。所制备的目标产品达到了实验的设计的预期目标，期望这些K2O-Bi2O3-BaO改性3D多孔碳吸附材料可以用于含铅离子的工业污水废水环境治理中。In the invention, the prepared 3D porous carbon is used as the main carrier material, K 2 O-Bi 2 O 3 -BaO with a certain content and composition is used as the filler of the adsorption material, and the composite adsorption with excellent performance is prepared by the newly developed ultrasonic-microwave combination method. Material. At the same time, the porous carbon adsorbents were modified by doping K 2 O-Bi 2 O 3 -BaO with different molar ratios. The modified porous carbon composite adsorbents were characterized by means of XRD and SEM. Through the comparison of microstructure and composition, a series of modified porous carbon composite adsorbents were selected, and their adsorption properties were studied and analyzed, and a better composite 3D porous carbon composite adsorbent material was obtained. It was found that the adsorption amount, removal time and material composition of the series of porous carbon composites with different compositions were different for the heavy metal ion solution containing Pb(Ⅱ) ions. The results showed that the K 2 O-Bi 2 O 3 -BaO (1:2:1) modified 3D porous carbon (70%) had the best adsorption effect, and the adsorption amount reached 239 mg/g. The prepared target products reach the expected goal of the experimental design, and it is expected that these K 2 O-Bi 2 O 3 -BaO modified 3D porous carbon adsorption materials can be used in the environmental treatment of industrial sewage wastewater containing lead ions.
附图说明Description of drawings
以下结合实施例和附图对本发明的改性3D多孔碳复合吸附材料的制备方法作出进一步的详述。The preparation method of the modified 3D porous carbon composite adsorption material of the present invention will be further described in detail below with reference to the examples and the accompanying drawings.
图1是实施例1～10制备各系列复合吸附材料的XRD图。Fig. 1 is the XRD pattern of each series of composite adsorbent materials prepared in Examples 1-10.
图2依次是实施例1制备复合吸附材料的低、中、高倍率SEM图。FIG. 2 is the low, medium and high magnification SEM images of the composite adsorption material prepared in Example 1 in turn.
图3是实施例1～7制备各系列复合吸附材料的吸附残余铅离子百分比曲线图。3 is a graph showing the percentage of adsorption residual lead ions of various series of composite adsorption materials prepared in Examples 1 to 7.
图4是实施例1～7制备各系列复合吸附材料的吸附量曲线图。4 is a graph showing the adsorption capacity of each series of composite adsorbents prepared in Examples 1-7.
具体实施方式Detailed ways
实施例1Example 1
本实施中，制得的改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO中，C、K2O、Bi2O3和BaO的掺杂摩尔比为7：1：2：1。制备方法步骤如下：In this implementation, in the prepared modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO, the doping molar ratio of C, K 2 O, Bi 2 O 3 and BaO is 7:1:2 :1. The preparation method steps are as follows:
1)、按照摩尔比称取硝酸钾、硝酸钡、硝酸铋加入烧杯中，使用蒸馏水溶解，磁力搅拌下加入氨水调节溶液的pH值至12，充分搅拌后，用氨水溶液调其pH。1), weigh potassium nitrate, barium nitrate, bismuth nitrate according to the molar ratio and add it to the beaker, use distilled water to dissolve, add ammonia water to adjust the pH value of the solution to 12 under magnetic stirring, after fully stirring, adjust its pH with ammonia solution.
2)、将竹木活性炭粉球磨均匀颗粒至1μm的细粉，然后加入至溶液中，充分搅拌后，再次用氨水溶液调其pH至12。2), the bamboo and wood activated carbon powder is ball-milled to a fine powder of 1 μm, and then added to the solution, after fully stirring, the pH is adjusted to 12 with ammonia solution again.
3)、将溶液置于超声波微波组合反应器中进行反应，采用超声波1200W+微波1000W双功能化反应30min。3), place the solution in an ultrasonic microwave combined reactor for reaction, and adopt ultrasonic 1200W+microwave 1000W bifunctional reaction for 30min.
4)、反应结束后，将样品放入150℃烘箱中干燥6h，获得改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO(7-1-2-1)。4) After the reaction, put the sample into a 150° C. oven to dry for 6 hours to obtain a modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO (7-1-2-1).
实施例2Example 2
本实施例中，制得的改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO中，C、K2O、Bi2O3和BaO的掺杂摩尔比为7：1：1：1，制备方法同实施例1，获得改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO(7-1-1-1)。In this example, in the prepared modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO, the doping molar ratio of C, K 2 O, Bi 2 O 3 and BaO is 7:1: 1:1, the preparation method was the same as that of Example 1, and the modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO (7-1-1-1) was obtained.
实施例3Example 3
本实施例中，制得的改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO中，C、K2O、Bi2O3和BaO的掺杂摩尔比为7：1：1：2，制备方法同实施例1，获得改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO(7-1-1-2)。In this example, in the prepared modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO, the doping molar ratio of C, K 2 O, Bi 2 O 3 and BaO is 7:1: 1:2, the preparation method was the same as that of Example 1, and the modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO (7-1-1-2) was obtained.
实施例4Example 4
本实施例中，制得的改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO中，C、K2O、Bi2O3和BaO的掺杂摩尔比为7：1：2：2，制备方法同实施例1，获得改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO(7-1-2-2)。In this example, in the prepared modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO, the doping molar ratio of C, K 2 O, Bi 2 O 3 and BaO is 7:1: 2:2, the preparation method was the same as that of Example 1, and the modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO (7-1-2-2) was obtained.
实施例5Example 5
本实施例中，制得的改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO中，C、K2O、Bi2O3和BaO的掺杂摩尔比为7：2：1：1，制备方法同实施例1，获得改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO(7-2-1-1)。In this example, in the prepared modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO, the doping molar ratio of C, K 2 O, Bi 2 O 3 and BaO is 7:2: 1:1, the preparation method was the same as that of Example 1, and the modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO (7-2-1-1) was obtained.
实施例6Example 6
本实施例中，制得的改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO中，C、K2O、Bi2O3和BaO的掺杂摩尔比为7：2：1：2，制备方法同实施例1，获得改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO(7-2-1-2)。In this example, in the prepared modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO, the doping molar ratio of C, K 2 O, Bi 2 O 3 and BaO is 7:2: 1:2, the preparation method is the same as that of Example 1, and the modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO (7-2-1-2) is obtained.
实施例7Example 7
本实施例中，制得的改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO中，C、K2O、Bi2O3和BaO的掺杂摩尔比为7：2：2：1，制备方法同实施例1，获得改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO(7-2-2-1)。In this example, in the prepared modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO, the doping molar ratio of C, K 2 O, Bi 2 O 3 and BaO is 7:2: 2:1, the preparation method was the same as that of Example 1, and the modified 3D porous carbon composite adsorption material CK 2 O-Bi 2 O 3 -BaO (7-2-2-1) was obtained.
实施例8Example 8
本实施例中，仅掺杂Bi2O3，制备原料中不含有硝酸钾、硝酸钡，C和Bi2O3的掺杂摩尔比为7：3，其他步骤同实施例1，获得改性3D多孔碳复合吸附材料C-Bi2O3(7-3)。In this example, only Bi 2 O 3 is doped, the preparation raw materials do not contain potassium nitrate and barium nitrate, the doping molar ratio of C and Bi 2 O 3 is 7:3, and other steps are the same as in Example 1, to obtain modified 3D porous carbon composite adsorption material C-Bi 2 O 3 (7-3).
实施例9Example 9
本实施例中，仅掺杂BaO，制备原料中不含有硝酸钾、硝酸铋，C和BaO的掺杂摩尔比为7：3，其他步骤同实施例1，获得改性3D多孔碳复合吸附材料C-BaO(7-3)。In this example, only BaO is doped, the preparation raw materials do not contain potassium nitrate and bismuth nitrate, the doping molar ratio of C and BaO is 7:3, and other steps are the same as in Example 1, to obtain a modified 3D porous carbon composite adsorption material C-BaO (7-3).
实施例10Example 10
本实施例中，仅掺杂K2O，制备原料中不含有硝酸钡、硝酸铋，C和K2O的掺杂摩尔比为7：3，其他步骤同实施例1，获得改性3D多孔碳复合吸附材料C-K2O(7-3)。In this example, only K 2 O is doped, the preparation raw materials do not contain barium nitrate and bismuth nitrate, the doping molar ratio of C and K 2 O is 7:3, and other steps are the same as in Example 1 to obtain a modified 3D porous Carbon composite adsorbent CK 2 O (7-3).
图1是实施例1～10制备各系列复合吸附材料的XRD图。由图1可知，样品的衍射强峰与C-K2O-Bi2O3-BaO物相基本相对应，系列衍射谱图衍射峰出峰位置基本一致，峰强相比较有明显的差异，XRD衍射图有明显的Bi2O3，BaO，K2O的衍射峰，而且都比较尖锐，说明合成的复合吸附剂在物相上与实验设计目标物3D多孔C-K2O-Bi2O3-BaO相吻合。Fig. 1 is the XRD pattern of each series of composite adsorbent materials prepared in Examples 1-10. It can be seen from Figure 1 that the diffraction intensity peaks of the sample basically correspond to the CK 2 O-Bi 2 O 3 -BaO phase. The positions of the diffraction peaks in the series of diffraction spectra are basically the same, and the peak intensity is obviously different. The XRD diffraction There are obvious diffraction peaks of Bi 2 O 3 , BaO and K 2 O in the figure, and they are all sharp, indicating that the synthesized composite adsorbent is in phase with the experimental design target 3D porous CK 2 O-Bi 2 O 3 -BaO match.
图2依次是实施例1制备复合吸附材料的低、中、高倍率SEM图。从图2可知，本实施例获得的改性3D多孔碳复合吸附材料C-K2O-Bi2O3-BaO(7-1-2-1)是由片形、棒状、四面体状等形状而组成的多孔结构，复合材料的微结构尺寸范围在500nm-2um之间。FIG. 2 is the low, medium and high magnification SEM images of the composite adsorption material prepared in Example 1 in turn. It can be seen from FIG. 2 that the modified 3D porous carbon composite adsorbent CK 2 O-Bi 2 O 3 -BaO (7-1-2-1) obtained in this example is composed of sheets, rods, tetrahedrons, etc. The composition of the porous structure, the microstructure size range of the composite material is between 500nm-2um.
图3为日光照条件下，实施例1～7制备不同组成的系列多孔碳复合材料对含Pb(Ⅱ)离子重金属离子溶液去除率的影响。其中，改性3D多孔碳吸附材料的用量为30mg，吸附时间为150min，Pb(Ⅱ)溶液体积为100mL，初始浓度均为100mg/L。由图3可知，实施例1制备C-K2O-Bi2O3-BaO(7-1-2-1)的吸附效果最好，去除率达到99.8％，且所有不同组成的系列产品在随时间的延长，吸附去除效果越好。Figure 3 shows the effects of the series of porous carbon composites with different compositions prepared in Examples 1 to 7 on the removal rate of heavy metal ion solutions containing Pb(II) ions under the condition of sunlight. Among them, the dosage of modified 3D porous carbon adsorption material was 30 mg, the adsorption time was 150 min, the volume of Pb(II) solution was 100 mL, and the initial concentration was 100 mg/L. It can be seen from Figure 3 that the adsorption effect of CK 2 O-Bi 2 O 3 -BaO (7-1-2-1) prepared in Example 1 is the best, and the removal rate reaches 99.8%, and all the series of products with different compositions increase with time. The longer the longer, the better the adsorption and removal effect.
图4为日光照条件下，实施例1～7制备不同不同组成的系列多孔碳复合材料对含Pb(Ⅱ)离子重金属离子溶液吸附量与去除时间、物质组成的曲线。其中，改性3D多孔碳吸附材料用量为50mg，吸附时间为140min，Pb(Ⅱ)溶液体积为500mL。由图4可知，实施例1制备C-K2O-Bi2O3-BaO(7-1-2-1)的吸附效果最好，吸附量达到239mg/g，且所有不同组成的系列产品在随时间的延长，吸附去除效果越好。同时，可以看出在吸附时间达到60分钟后，随着时间的增加，吸附量基本上达到稳定，说明吸附过程主要是在60分钟内完成，而且吸附效果很好。因此，通过实验证明本发明制备的C-K2O-Bi2O3-BaO改性3D多孔碳吸附材料可以用于含铅离子的工业污水废水环境治理中。Figure 4 shows the curves of adsorption amount, removal time and material composition of the series of porous carbon composites with different compositions prepared in Examples 1 to 7 to heavy metal ion solution containing Pb(II) ions under the condition of sunlight. Among them, the dosage of modified 3D porous carbon adsorption material was 50 mg, the adsorption time was 140 min, and the volume of Pb(Ⅱ) solution was 500 mL. It can be seen from Figure 4 that the adsorption effect of CK 2 O-Bi 2 O 3 -BaO (7-1-2-1) prepared in Example 1 is the best, and the adsorption amount reaches 239 mg/g, and all the series products with different compositions are The longer the time, the better the adsorption and removal effect. At the same time, it can be seen that after the adsorption time reaches 60 minutes, the adsorption amount is basically stable with the increase of time, indicating that the adsorption process is mainly completed within 60 minutes, and the adsorption effect is very good. Therefore, it is proved by experiments that the CK 2 O-Bi 2 O 3 -BaO modified 3D porous carbon adsorption material prepared by the present invention can be used in the environmental treatment of industrial sewage wastewater containing lead ions.
实施例11Example 11
本实施中，加入氨水调节pH值为10，其他步骤同实施例1。In this implementation, adding ammonia water to adjust the pH value is 10, and other steps are the same as in Example 1.
实施例12Example 12
本实施例中，将竹木活性炭替换为煤质活性炭粉，其他步骤同实施例1。In this embodiment, the bamboo and wood activated carbon is replaced with coal-based activated carbon powder, and other steps are the same as those in Embodiment 1.
实施例13Example 13
本实施例中，将竹木活性炭替换为椰壳活性炭粉，且球磨均匀颗粒至5μm的细粉，其他步骤同实施例1。In the present embodiment, the bamboo activated carbon is replaced with coconut shell activated carbon powder, and the uniform particles are ball-milled to a fine powder of 5 μm, and other steps are the same as those in Example 1.
以上内容仅仅是对本发明的构思所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离发明的构思或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。The above contents are only examples and descriptions of the concept of the present invention. Those skilled in the art can make various modifications or supplements to the described specific embodiments or replace them in similar ways, as long as they do not deviate from the concept of the invention. Or beyond the scope defined by the claims, shall belong to the protection scope of the present invention.
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