CN103936004A - Preparation method of resin-based spherical activated carbon with controllable pore structure - Google Patents
Preparation method of resin-based spherical activated carbon with controllable pore structure Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229920005989 resin Polymers 0.000 title claims abstract description 34
- 239000011347 resin Substances 0.000 title claims abstract description 34
- 239000011148 porous material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005011 phenolic resin Substances 0.000 claims abstract description 17
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 150000002989 phenols Chemical class 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 claims description 42
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- CYEKUDPFXBLGHH-UHFFFAOYSA-N 3-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1 CYEKUDPFXBLGHH-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229920000084 Gum arabic Polymers 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 241000978776 Senegalia senegal Species 0.000 claims description 4
- 239000000205 acacia gum Substances 0.000 claims description 4
- 235000010489 acacia gum Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 12
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 10
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 9
- 239000004312 hexamethylene tetramine Substances 0.000 description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
一种可控孔结构的树脂基球状活性炭的制备方法是将酚类与醛类按照摩尔比为1:2-6加入水中，将酚类摩尔量0.7%-1%的催化剂加入上述溶液中，在搅拌的条件下加热升温到85-90℃，然后添加酚类摩尔量10%-30%的分散剂，继续搅拌20-60分钟后加入酚类摩尔量1%-3%的固化剂和酚类摩尔量0-5%的造孔剂，继续搅拌2-5小时，冷却到室温，过滤得到树脂球；将制备的树脂球，在氮气保护炭化，再进行活化，降温至室温，得到酚醛树脂基球状活性炭。本发明具有孔径可控、操作条件温和、成本低廉的优点。A preparation method of a resin-based spherical activated carbon with a controllable pore structure is to add phenols and aldehydes to water according to a molar ratio of 1:2-6, and add a catalyst with a molar amount of phenols of 0.7%-1% to the above solution, Heat up to 85-90°C with stirring, then add a dispersant with 10%-30% phenolic molar mass, continue stirring for 20-60 minutes, then add curing agent and phenolic molar mass 1%-3% phenolic For a pore-forming agent with a molar mass of 0-5%, continue to stir for 2-5 hours, cool to room temperature, and filter to obtain resin balls; carbonize the prepared resin balls under nitrogen protection, then activate, cool to room temperature, and obtain phenolic resin Spherical activated carbon. The invention has the advantages of controllable pore size, mild operating conditions and low cost.
Description
技术领域technical field
本发明属于一种制备孔结构可控的酚醛树脂基球状活性炭的方法。The invention belongs to a method for preparing phenolic resin-based spherical activated carbon with controllable pore structure.
背景技术Background technique
球状活性炭具有良好的球形度、吸附量大、填充密度均匀、阻力小等优点，在催化、化工分离、环保、医疗等方面具有重要的作用。目前制备球状活性炭的原料包括沥青、酚醛树脂、聚苯乙烯球等。由于酚醛树脂的原料价廉易得，并且合成方便，炭化收率高，含杂质量低以及具有良好的机械强度和耐热性能，而成为制备球状活性炭的主要前驱体。Spherical activated carbon has the advantages of good sphericity, large adsorption capacity, uniform packing density, and low resistance. It plays an important role in catalysis, chemical separation, environmental protection, and medical treatment. At present, the raw materials for preparing spherical activated carbon include asphalt, phenolic resin, polystyrene balls, etc. Because the raw materials of phenolic resin are cheap and easy to obtain, and the synthesis is convenient, the carbonization yield is high, the impurity content is low, and it has good mechanical strength and heat resistance, it has become the main precursor for the preparation of spherical activated carbon.
杨俊兵（专利号CN98115717.3）等将酚醛树脂、固化剂、溶剂混合后，减压除去溶剂，再进行破碎、筛分得到预定粒度的颗粒，将此颗粒与加入表面活性剂的水溶液，利用乳化法制备树脂基小球，得到的树脂基小球再进行炭化、活化后得到酚醛树脂基球状活性炭，此方法过程复杂，重现性差。王芙蓉（专利号CN200410012346.X）以水和乙醇混合物为溶剂，聚乙烯醇为表面活性剂，加热酚醛树脂得到树脂小球，但是该方法适合于制备微米级小球，生产0.3mm以上的小球时球径分布变宽。李开喜（专利号101157451B）等将预处理料加入酚醛树脂的醇溶液中，再添加表面活性剂，混合物在高压釜中加热搅拌到110-140℃。以上这些方法都不能很好的调控球状活性炭的孔径，且在高压釜中反应，条件苛刻。Yang Junbing (Patent No. CN98115717.3) mixed the phenolic resin, curing agent, and solvent, removed the solvent under reduced pressure, and then crushed and sieved to obtain particles with a predetermined particle size. Resin-based pellets are prepared by this method, and the obtained resin-based pellets are then carbonized and activated to obtain phenolic resin-based spherical activated carbon. The process of this method is complicated and the reproducibility is poor. Wang Furong (Patent No. CN200410012346.X) used a mixture of water and ethanol as a solvent, polyvinyl alcohol as a surfactant, and heated phenolic resin to obtain resin pellets. Ball diameter distribution becomes wider. Li Kaixi (Patent No. 101157451B) and others added the pretreatment material to the alcohol solution of phenolic resin, and then added a surfactant, and the mixture was heated and stirred in an autoclave to 110-140°C. None of the above methods can well control the pore size of spherical activated carbon, and the reaction in an autoclave is harsh.
发明内容Contents of the invention
本发明的目的在于提供一种孔径可控、操作条件温和、成本低廉的酚醛树脂基球状活性炭制备方法。The object of the present invention is to provide a method for preparing phenolic resin-based spherical activated carbon with controllable pore size, mild operating conditions and low cost.
本发明实施过程如下：The implementation process of the present invention is as follows:
将酚类与醛类按照摩尔比为1:（2-6）加入水中，将酚类摩尔量0.7%-1%的催化剂加入上述溶液中，在搅拌的条件下加热升温到85-90℃，然后添加酚类摩尔量10%-30%的分散剂，继续搅拌20-60分钟后加入酚类摩尔量1%-3%的固化剂和酚类摩尔量0-5%的造孔剂，继续搅拌2-5小时，冷却到室温，过滤得到树脂球；将制备的树脂球，在氮气保护下由室温升温至700-1000℃炭化，然后再通入二氧化碳或水蒸气进行活化，自然降温至室温，得到酚醛树脂基球状活性炭。Add phenols and aldehydes to water according to the molar ratio of 1: (2-6), add a catalyst with a molar weight of 0.7%-1% phenols into the above solution, heat up to 85-90°C under stirring conditions, Then add a dispersing agent with a molar weight of 10%-30% of phenols, continue to stir for 20-60 minutes, then add a curing agent with a molar weight of phenols of 1%-3% and a pore-forming agent with a molar weight of phenols of 0-5%, and continue Stir for 2-5 hours, cool to room temperature, and filter to obtain resin balls; carbonize the prepared resin balls from room temperature to 700-1000°C under the protection of nitrogen, then pass in carbon dioxide or water vapor for activation, and cool down to room temperature naturally , to obtain phenolic resin-based spherical activated carbon.
如上所述所用酚类为间乙苯酚、间叔丁基苯酚、1-萘酚、1,5-二羟基萘中的一种或者多种混合；醛类为甲醛、多聚甲醛；催化剂为三乙胺、氨水、氢氧化钠、氢氧化钡；分散剂为聚乙烯醇、十二烷基磺酸钠、阿拉伯胶；固化剂为六甲基四胺、三聚氰胺、苯胺；造孔剂为聚乙二醇、乙二醇。As mentioned above, the phenols used are one or more mixtures of m-ethylphenol, m-tert-butylphenol, 1-naphthol, and 1,5-dihydroxynaphthalene; the aldehydes are formaldehyde and paraformaldehyde; the catalyst is three Ethylamine, ammonia water, sodium hydroxide, barium hydroxide; dispersant is polyvinyl alcohol, sodium dodecyl sulfonate, gum arabic; curing agent is hexamethyltetramine, melamine, aniline; pore forming agent is polyethylene Diol, ethylene glycol.
如上所述的炭化条件是：升温速率为1-5℃/min，炭化温度为700-1000℃，炭化时间为0-1h。The carbonization conditions mentioned above are: the heating rate is 1-5°C/min, the carbonization temperature is 700-1000°C, and the carbonization time is 0-1h.
如上所述的活化条件是：活化温度为700-1000℃，活化时间为1-3h。The above-mentioned activation conditions are: the activation temperature is 700-1000°C, and the activation time is 1-3h.
本发明的优点Advantages of the invention
1、从分子层面控制球状活性炭的孔径。1. Control the pore size of spherical activated carbon from the molecular level.
2、成本低廉，以更基础的原料来制备酚醛树脂球。2. The cost is low, and the phenolic resin balls are prepared with more basic raw materials.
3、操作条件温和，成球反应在常压下进行。3. The operating conditions are mild, and the ball forming reaction is carried out under normal pressure.
具体实施方式Detailed ways
实施例1Example 1
将间乙苯酚与甲醛按照摩尔比为1:4加入水中，将间乙苯酚摩尔量0.75%的三乙胺加入上述溶液中，在搅拌的条件下加热升温到85℃，然后添加间乙苯酚摩尔量23%的聚乙烯醇，继续搅拌30分钟后加入间乙苯酚摩尔量3%的六次甲基四胺和间乙苯酚摩尔量2.5%的乙二醇，继续搅拌3小时，冷却到室温后，过滤得到树脂球。将制备的树脂球，在氮气保护下由室温升温至850℃炭化1h，然后再通入水蒸气进行活化2h，自然降温至室温，得到酚醛树脂基球状活性炭。Add m-ethylphenol and formaldehyde into water at a molar ratio of 1:4, add triethylamine with a molar mass of m-ethylphenol of 0.75% to the above solution, heat up to 85°C while stirring, and then add m-ethylphenol molar Measure 23% polyvinyl alcohol, continue to stir for 30 minutes, add hexamethylenetetramine with 3% m-ethylphenol molar weight and ethylene glycol with 2.5% m-ethylphenol molar weight, continue to stir for 3 hours, after cooling to room temperature , and filtered to obtain resin balls. The prepared resin balls were carbonized from room temperature to 850 °C for 1 h under the protection of nitrogen, then activated by passing water vapor for 2 h, and cooled down to room temperature naturally to obtain phenolic resin-based spherical activated carbon.
实施例2Example 2
将间乙苯酚与甲醛按照摩尔比为1:4加入水中，将间乙苯酚摩尔量0.75%的三乙胺加入上述溶液中，在搅拌的条件下加热升温到90℃，然后添加间乙苯酚摩尔量23%的聚乙烯醇，继续搅拌30分钟后加入间乙苯酚摩尔量3%的六次甲基四胺和间乙苯酚摩尔量2.8%的聚乙二醇，继续搅拌3小时，冷却到室温后，过滤得到树脂球。将制备的树脂球，在氮气保护下由室温升温至1000℃炭化1h，然后再通入水蒸气进行活化2h，自然降温至室温，得到酚醛树脂基球状活性炭，其孔结构特性见表1。Add m-ethylphenol and formaldehyde into water at a molar ratio of 1:4, add triethylamine with a molar mass of m-ethylphenol of 0.75% to the above solution, heat up to 90°C while stirring, and then add m-ethylphenol molar Measure 23% polyvinyl alcohol, continue to stir for 30 minutes, add hexamethylenetetramine with a molar weight of m-ethylphenol of 3% and polyethylene glycol with a molar weight of m-ethylphenol of 2.8%, continue to stir for 3 hours, and cool to room temperature Finally, filter to obtain resin balls. The prepared resin spheres were carbonized from room temperature to 1000°C under the protection of nitrogen for 1 h, then activated by passing water vapor for 2 h, and cooled down to room temperature naturally to obtain phenolic resin-based spherical activated carbon. The pore structure characteristics are shown in Table 1.
实施例3Example 3
将间乙苯酚与甲醛按照摩尔比为1:2加入水中，将间乙苯酚摩尔量0.85%三乙胺加入上述溶液中，在搅拌的条件下加热升温到90℃，然后添加间乙苯酚摩尔量23%的聚乙烯醇，继续搅拌60分钟后加入间乙苯酚摩尔量3%的六次甲基四胺，继续搅拌2小时，冷却到室温后，过滤得到树脂球。将制备的树脂球，在氮气保护下由室温升温至700℃，不炭化，然后再通入水蒸气进行活化1h，自然降温至室温，得到酚醛树脂基球状活性炭，其孔结构特性见表1。Add m-ethylphenol and formaldehyde into water according to the molar ratio of 1:2, add m-ethylphenol molar amount of 0.85% triethylamine into the above solution, heat up to 90°C while stirring, and then add m-ethylphenol molar amount 23% polyvinyl alcohol, continue to stir for 60 minutes, add hexamethylenetetramine with a molar weight of m-ethylphenol of 3%, continue to stir for 2 hours, cool to room temperature, and filter to obtain resin balls. The prepared resin balls were heated from room temperature to 700 °C under the protection of nitrogen without carbonization, and then activated by passing water vapor for 1 h, and then cooled down to room temperature naturally to obtain phenolic resin-based spherical activated carbon. The pore structure characteristics are shown in Table 1.
实施例4Example 4
将间叔丁基苯酚与甲醛按照摩尔比为1:6加入水中，将间叔丁基苯酚摩尔量0.75%的氨水加入上述溶液中，在搅拌的条件下加热升温到90℃，然后添加间叔丁基苯酚摩尔量30%的十二烷基磺酸钠，继续搅拌20分钟后加入间叔丁基苯酚摩尔量1%的三聚氰胺，继续搅拌5小时，冷却到室温后，过滤得到树脂球。将制备的树脂球，在氮气保护下由室温升温至900℃炭化1h，然后再通入CO2进行活化2h，自然降温至室温，得到酚醛树脂基球状活性炭，其孔结构特性见表1。Add m-tert-butylphenol and formaldehyde into water at a molar ratio of 1:6, add ammonia water with a molar mass of m-tert-butylphenol of 0.75% to the above solution, heat up to 90°C while stirring, and then add m-tert-butylphenol Sodium dodecylsulfonate with 30% molar mass of butylphenol, continued to stir for 20 minutes, then added melamine with 1% molar mass of m-tert-butylphenol, continued to stir for 5 hours, cooled to room temperature, and filtered to obtain resin balls. The prepared resin balls were carbonized from room temperature to 900 °C for 1 h under the protection of nitrogen, and then activated by passing CO2 for 2 h, and then cooled down to room temperature naturally to obtain phenolic resin-based spherical activated carbon. The pore structure characteristics are shown in Table 1.
实施例5Example 5
将1-萘酚与多聚甲醛按照摩尔比为1:5加入水中，将1-萘酚摩尔量1%的氨水加入上述溶液中，在搅拌的条件下加热升温到90℃，然后添加1-萘酚摩尔量20%的阿拉伯胶，继续搅拌30分钟后加入1-萘酚摩尔量12%的苯胺，1-萘酚摩尔量15%的乙二醇，继续搅拌3小时，冷却到室温后，过滤得到树脂球。将制备的树脂球，在氮气保护下由室温升温至800℃炭化2h，然后再通入CO2进行活化3h，自然降温至室温，得到酚醛树脂基球状活性炭，其孔结构特性见表1。Add 1-naphthol and paraformaldehyde into water according to the molar ratio of 1:5, add 1-naphthol molar amount of 1% ammonia water into the above solution, heat up to 90°C while stirring, and then add 1- The gum arabic of naphthol molar weight 20%, after continuing to stir for 30 minutes, add the aniline of 1-naphthol molar weight 12%, the ethylene glycol of 1-naphthol molar weight 15%, continue to stir 3 hours, after being cooled to room temperature, Filter to obtain resin balls. The prepared resin balls were carbonized from room temperature to 800°C for 2 h under the protection of nitrogen, and then activated with CO 2 for 3 h, and cooled down to room temperature naturally to obtain phenolic resin-based spherical activated carbon. The pore structure characteristics are shown in Table 1.
实施例6Example 6
将1,5-二羟基萘与甲醛按照摩尔比为1:2加入水中，将1,5-二羟基萘摩尔量0.8%的氢氧化钡加入上述溶液中，在搅拌的条件下加热升温到90℃，然后添加1,5-二羟基萘摩尔量10%的聚乙烯醇，继续搅拌30分钟后加入1,5-二羟基萘摩尔量2%的六次甲基四胺，1,5-二羟基萘摩尔量5%的聚乙二醇，继续搅拌5小时，冷却到室温后，过滤得到树脂球。将制备的树脂球，在氮气保护下由室温升温至900摄氏度炭化1h，然后再通入水蒸气进行活化2h，自然降温至室温，得到酚醛树脂基球状活性炭，其孔结构特性见表1。Add 1,5-dihydroxynaphthalene and formaldehyde into water at a molar ratio of 1:2, add barium hydroxide with a molar weight of 0.8% of 1,5-dihydroxynaphthalene to the above solution, and heat to 90 ℃, then add polyvinyl alcohol with 10% molar weight of 1,5-dihydroxynaphthalene, continue stirring for 30 minutes, then add hexamethylenetetramine with 2% molar weight of 1,5-dihydroxynaphthalene, 1,5-dihydroxy naphthalene Polyethylene glycol with 5% molar amount of hydroxynaphthalene was stirred for 5 hours, cooled to room temperature, and filtered to obtain resin balls. The prepared resin spheres were carbonized under the protection of nitrogen from room temperature to 900 °C for 1 h, then activated by passing water vapor for 2 h, and cooled down to room temperature naturally to obtain phenolic resin-based spherical activated carbon. The pore structure characteristics are shown in Table 1.
实施例7Example 7
将1-萘酚与多聚甲醛按照摩尔比为1:3加入水中，将1-萘酚摩尔量10%的三乙胺加入上述溶液中，在搅拌的条件下加热升温到90℃，然后添加1-萘酚摩尔量30%的阿拉伯胶，继续搅拌30分钟后加入1-萘酚摩尔量1%的三聚氰胺，继续搅拌3小时，冷却到室温后，过滤得到树脂球。将制备的树脂球，在氮气保护下由室温升温至800℃炭化2h，然后再通入CO2进行活化3h，自然降温至室温，得到酚醛树脂基球状活性炭，其孔结构特性见表1。Add 1-naphthol and paraformaldehyde into water at a molar ratio of 1:3, add triethylamine with 10% molar weight of 1-naphthol to the above solution, heat up to 90°C under stirring, and then add Gum Arabic with 1-naphthol molar weight 30%, continue to stir for 30 minutes, add melamine with 1-naphthol molar weight 1%, continue stirring for 3 hours, cool to room temperature, and filter to obtain resin balls. The prepared resin balls were carbonized from room temperature to 800°C for 2 h under the protection of nitrogen, and then activated with CO 2 for 3 h, and cooled down to room temperature naturally to obtain phenolic resin-based spherical activated carbon. The pore structure characteristics are shown in Table 1.
实施例8Example 8
将间乙苯酚与多聚甲醛按照摩尔比为1:6加入水中，将间乙苯酚摩尔量0.75%的三乙胺加入上述溶液中，在搅拌的条件下加热升温到90℃，然后添加间乙苯酚摩尔量23%的聚乙烯醇，继续搅拌30分钟后加入间乙苯酚摩尔量3%的六次甲基四胺和间乙苯酚摩尔量2.5%的乙二醇，继续搅拌3小时，冷却到室温后，过滤得到树脂球。将制备的树脂球，在氮气保护下由室温升温至850℃炭化1h，然后再通入水蒸气进行活化2h，自然降温至室温，得到酚醛树脂基球状活性炭，其孔结构特性见表1。Add m-ethylphenol and paraformaldehyde into water at a molar ratio of 1:6, add m-ethylphenol molar mass of 0.75% triethylamine into the above solution, heat up to 90°C under stirring, and then add m-ethylphenol The polyvinyl alcohol of phenol molar weight 23%, continue to stir 30 minutes, add the hexamethylenetetramine of m-ethylphenol molar weight 3% and the ethylene glycol of m-ethylphenol molar weight 2.5%, continue to stir 3 hours, be cooled to After room temperature, the resin balls were obtained by filtration. The prepared resin balls were carbonized from room temperature to 850°C under the protection of nitrogen for 1 h, then activated by passing water vapor for 2 h, and cooled down to room temperature naturally to obtain phenolic resin-based spherical activated carbon. The pore structure characteristics are shown in Table 1.
实施例9Example 9
将1,5-二羟基萘与多聚甲醛按照摩尔比为1:4加入水中，将1,5-二羟基萘摩尔量0.8%的三乙胺加入上述溶液中，在搅拌的条件下加热升温到90℃，然后添加1,5-二羟基萘摩尔量23%的聚乙烯醇，继续搅拌30分钟后加入1,5-二羟基萘摩尔量3%的六次甲基四胺和1,5-二羟基萘摩尔量5%的聚乙二醇，继续搅拌3小时，冷却到室温后，过滤得到树脂球。将制备的树脂球，在氮气保护下由室温升温至850℃炭化1.5h，然后再通入水蒸气进行活化1.5h，自然降温至室温，得到酚醛树脂基球状活性炭，其孔结构特性见表1。Add 1,5-dihydroxynaphthalene and paraformaldehyde into water at a molar ratio of 1:4, add triethylamine with a molar weight of 0.8% of 1,5-dihydroxynaphthalene to the above solution, and heat up while stirring to 90°C, then add polyvinyl alcohol with a molar weight of 23% of 1,5-dihydroxynaphthalene, continue stirring for 30 minutes, and then add hexamethylenetetramine with a molar weight of 1,5-dihydroxynaphthalene of 3% and 1,5 -Polyethylene glycol with 5% dihydroxynaphthalene molar weight, continue to stir for 3 hours, after cooling to room temperature, filter to obtain resin balls. The prepared resin spheres were heated from room temperature to 850°C for 1.5 h under the protection of nitrogen, then activated by passing water vapor for 1.5 h, and cooled down to room temperature naturally to obtain phenolic resin-based spherical activated carbon. The pore structure characteristics are shown in Table 1.
表1制备球状活性炭的孔结构特性Table 1 Pore structure characteristics of prepared spherical activated carbon
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| CN108862240A (en) * | 2018-07-31 | 2018-11-23 | 大连理工大学 | A kind of heteroatom-doped carbon nano-microsphere and its preparation method |
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