CN102442665A - Heat-treated activated carbon and preparation method thereof - Google Patents
Heat-treated activated carbon and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- -1 steam Chemical compound 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 24
- 239000003054 catalyst Substances 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种热处理活性炭及其制备方法，将经过高温处理后的活性炭与扩孔剂混合均匀，于300-1000℃扩孔处理0.1-48小时得中孔和大孔率高的热处理活性炭。采用本发明得到的活性炭具有处理过程炭烧失率低，微孔孔容与总孔容的比值低，中孔率和大孔率高这些优点，能够作为催化剂的载体。The invention discloses a heat-treated activated carbon and a preparation method thereof. The activated carbon treated at high temperature is mixed evenly with a pore-enlarging agent, and the pore-enlarging treatment is performed at 300-1000°C for 0.1-48 hours to obtain the heat-treated activated carbon with high mesopore and macropore rates. The activated carbon obtained by the invention has the advantages of low carbon burning loss rate during the treatment process, low ratio of micropore volume to total pore volume, high mesopore and macropore rates, and can be used as a catalyst carrier.
Description
技术领域 technical field
本发明涉及一种中孔和大孔率高的热处理活性炭及其制备方法，属于材料科学领域。 The invention relates to heat-treated activated carbon with high mesopore and macroporosity and a preparation method thereof, belonging to the field of material science.
背景技术 Background technique
活性炭广泛地被应用为催化剂的载体，普通活性炭微孔发达，比表面积高，但是存在中孔数量少的缺点。同时炭载体比表面积太高或者微孔数量太多会导致所负载的活性金属粒子太小，将不利于一些催化反应的进行，降低了活性金属的利用率。如许多文献报道了在氨合成反应中，增加活性炭载体的中孔率和大孔率将有助于提高钌催化剂的氨合成活性。此外，在一些反应体系中，普通活性炭的稳定性不足，这极大地影响催化剂的寿命。比如活性炭是钌系氨合成催化剂最理想的载体，但是在高温含氢的气氛中活性炭也会被钌催化发生甲烷化反应。为了提高催化剂的稳定性和抗甲烷化能力，通常需要在惰性气氛中高温热处理活性炭载体使之产生石墨化结构。但是高温热处理会极大降低活性炭的比表面积和孔容、破坏载体的孔分布，从而不利于活性金属和助剂的分散。中国专利CN1382527介绍一种负载型钌催化剂中活性炭载体的扩孔方法，是将热处理后的活性炭在在混合气气氛中（氧气和氮气混合气、或者氮气和水蒸气混合气）进行扩孔处理。中国专利CN1544146描述了热处理后的活性炭在含有水蒸气及含氧气体的混合气中热处理的扩孔方法。这两种方法的本质都是利用含氧气体将炭载体表面的部分活泼的碳原子气化除去获得新孔。为了扩大活性炭载体的孔径，需要在扩孔处理时增加炭的烧失率（处理过程中炭载体质量减少的百分数），只有在较高的失炭量时才能生成部分中孔和大孔（在本发明的上下文中，术语“微孔”指的是孔径最多2nm（包括2nm）的孔；术语“中孔”指的是孔径范围大于2nm到50nm（包括50nm）的孔，术语“大孔”指的是孔径大于50nm的孔），此时也会导致活性炭的机械强度变差。Zhu等人在Influence of oxidation on heat-treated activated carbon support properties and metallic dispersion of Ru/C catalyst (Catalysis Letters, 2007, 115, 13-18.)中报道了不同气氛中不同处理时间的扩孔处理对热处理后的活性炭载体的失炭率和表面织构参数，发现将商业活性炭在氩气中经过1900℃处理2个小时后，再以二氧化碳为氧化剂、在850℃处理3小时所得到炭载体烧失率为23.4%，微孔孔容与总孔容比值最低为0.46。增加处理时间改变处理温度以及改变所使用的含氧气体种类都使样品的烧失率进一步增加，微孔孔容与总孔容比值增大，中孔率和大孔率减少。 Activated carbon is widely used as a catalyst carrier. Ordinary activated carbon has developed micropores and a high specific surface area, but has the disadvantage of a small number of mesopores. At the same time, if the specific surface area of the carbon carrier is too high or the number of micropores is too large, the supported active metal particles will be too small, which will not be conducive to the progress of some catalytic reactions and reduce the utilization rate of the active metal. As reported in many literatures, in the ammonia synthesis reaction, increasing the mesoporosity and macroporosity of the activated carbon support will help to improve the ammonia synthesis activity of the ruthenium catalyst. In addition, in some reaction systems, the stability of ordinary activated carbon is insufficient, which greatly affects the lifetime of the catalyst. For example, activated carbon is the most ideal carrier for ruthenium-based ammonia synthesis catalysts, but activated carbon will also be catalyzed by ruthenium to undergo methanation reaction in a high-temperature hydrogen-containing atmosphere. In order to improve the stability and resistance to methanation of the catalyst, it is usually necessary to heat-treat the activated carbon support at high temperature in an inert atmosphere to produce a graphitized structure. However, high-temperature heat treatment will greatly reduce the specific surface area and pore volume of activated carbon, and destroy the pore distribution of the carrier, which is not conducive to the dispersion of active metals and additives. Chinese patent CN1382527 introduces a pore-enlarging method for activated carbon carriers in supported ruthenium catalysts. The heat-treated activated carbon is subjected to pore-enlargement treatment in a mixed gas atmosphere (mixed gas of oxygen and nitrogen, or mixed gas of nitrogen and water vapor). Chinese patent CN1544146 describes a pore-enlarging method in which heat-treated activated carbon is heat-treated in a mixed gas containing water vapor and oxygen-containing gas. The essence of these two methods is to use oxygen-containing gas to gasify and remove some active carbon atoms on the surface of the carbon support to obtain new pores. In order to expand the pore size of the activated carbon carrier, it is necessary to increase the carbon loss rate (the percentage of carbon carrier mass reduction during the treatment process) during the pore expansion treatment. Only when the carbon loss is high can some mesopores and macropores (in the In the context of the present invention, the term "micropore" refers to pores with a diameter of up to 2nm (including 2nm); the term "mesopore" refers to pores with a diameter ranging from greater than 2nm to 50nm (inclusive), and the term "macropore" Refers to pores with a pore size greater than 50nm), which will also lead to poor mechanical strength of activated carbon. In Influence of oxidation on heat-treated activated carbon support properties and metallic dispersion of Ru/C catalyst (Catalysis Letters, 2007, 115, 13-18.), Zhu et al. reported the effect of reaming treatment in different atmospheres with different treatment times. The carbon loss rate and surface texture parameters of the activated carbon carrier after heat treatment, found that the commercial activated carbon was treated in argon at 1900°C for 2 hours, and then carbon dioxide was used as the oxidant at 850°C for 3 hours. The rate is 23.4%, and the ratio of micropore volume to total pore volume is the lowest at 0.46. Increasing the treatment time, changing the treatment temperature and changing the type of oxygen-containing gas used will further increase the loss on ignition rate of the sample, increase the ratio of micropore volume to total pore volume, and decrease the mesoporosity and macroporosity.
发明内容 Contents of the invention
本发明的目的在于提供一种中孔和大孔率高的热处理活性炭及其制备方法，该活性炭具有处理过程炭烧失率低，微孔孔容与总孔容的比值低，中孔率和大孔率高这些优点，能够作为催化剂的载体。 The object of the present invention is to provide a heat-treated activated carbon with high mesopore and macroporosity and a preparation method thereof. These advantages of high porosity can be used as a catalyst carrier.
为实现上述目的，本发明采用如下技术方案： To achieve the above object, the present invention adopts the following technical solutions:
一种热处理活性炭具有高的中孔和大孔率，该活性炭至少72%的总孔体积是由孔径大于2nm的孔（即中孔和大孔）形成的。其制备方法：将经过高温处理后的活性炭通过浸渍或机械混合的方法与扩孔剂混合均匀，110-130℃干燥4-6小时，于300-1000℃扩孔处理0.1-48小时，洗涤烘干后即得所述的高的中孔和大孔率的热处理活性炭。 A heat-treated activated carbon with high mesopore and macroporosity, at least 72% of the total pore volume of the activated carbon is formed by pores with a diameter greater than 2nm (ie mesopore and macropore). Its preparation method: mix the activated carbon after high temperature treatment with the pore-enlarging agent evenly by impregnation or mechanical mixing, dry at 110-130°C for 4-6 hours, expand the pores at 300-1000°C for 0.1-48 hours, wash and dry After drying, the heat-treated activated carbon with high mesopore and macroporosity is obtained.
所述的高温处理在惰性气体中进行，处理温度是1600-2500℃，时间是0.5-6小时。 The high temperature treatment is carried out in an inert gas, the treatment temperature is 1600-2500° C., and the time is 0.5-6 hours.
所述的扩孔剂是氢氧化钠、碳酸钠、氢氧化钾、碳酸钾、氯化铝、氯化镁、氯化锌、磷酸中的一种或多种任意比例的混合物。扩孔剂与活性炭的质量比是0.1-10:1。 The pore-enlarging agent is a mixture of one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, aluminum chloride, magnesium chloride, zinc chloride, and phosphoric acid in any proportion. The mass ratio of pore expander to activated carbon is 0.1-10:1.
所述的扩孔处理是在氮气、氧气、空气、水蒸气、二氧化碳、0族惰性气体的一种或多种任意比例的混合气体下进行的，气体的流速为5-1000mL/min。 The pore-enlarging treatment is carried out under one or more mixed gases in any proportion of nitrogen, oxygen, air, water vapor, carbon dioxide, and group 0 inert gases, and the flow rate of the gas is 5-1000mL/min.
所述的洗涤是先用稀盐酸、稀硝酸或者稀硫酸洗涤，然后用蒸馏水洗涤至洗涤液呈中性且不含酸性离子。 The washing is firstly washed with dilute hydrochloric acid, dilute nitric acid or dilute sulfuric acid, and then washed with distilled water until the washing solution is neutral and does not contain acid ions.
所述的烘干的温度80-150℃、时间2-30小时。 The drying temperature is 80-150° C. and the drying time is 2-30 hours.
本发明的显著优点在于：本发明的活性炭具有处理过程炭烧失率低，微孔孔容与总孔容的比值低（其值不大于0.28），中孔率和大孔率高（活性炭中72%以上的总孔体积是由孔径大于2nm的孔形成）等优点，能够作为催化剂的载体。 The remarkable advantages of the present invention are: the activated carbon of the present invention has a low carbon loss rate in the treatment process, a low ratio of micropore volume to total pore volume (the value is not more than 0.28), and high mesopore and macroporosity (in activated carbon More than 72% of the total pore volume is formed by pores with a diameter greater than 2nm), and can be used as a catalyst carrier.
具体实施方式 Detailed ways
以下以具体实施例来说明本发明的技术方案，但本发明的包括范围不限于此： The technical scheme of the present invention is illustrated below with specific examples, but the scope of the present invention is not limited thereto:
实施例1： Example 1:
取4g商业活性炭置于氩气中1850℃下处理1小时后，粉碎至12-16目，浸渍KOH溶液至KOH:C的质量比为0.5:1，于120℃下干燥4小时。将样品置于一管式炉内，在200 mL/min的氮气中于700℃扩孔处理2小时，在上述气氛中冷却至室温，先用20mL的稀盐酸（0.01 moL/L）洗涤5次，然后用蒸馏水洗涤至洗涤液呈中性且不含酸性离子，于烘箱中置于120干燥12小时。 Take 4g of commercial activated carbon and place it in argon at 1850°C for 1 hour, crush it to 12-16 mesh, impregnate it in KOH solution until the mass ratio of KOH:C is 0.5:1, and dry it at 120°C for 4 hours. Place the sample in a tube furnace, expand the pores at 700°C for 2 hours in 200 mL/min of nitrogen, cool to room temperature in the above atmosphere, and wash 5 times with 20 mL of dilute hydrochloric acid (0.01 moL/L) , and then washed with distilled water until the washing solution is neutral and free of acidic ions, and then dried in an oven at 120 for 12 hours.
实施例2： Example 2:
重复实施例1，只是将扩孔处理的时间从2小时延长至20小时。 Example 1 was repeated, except that the time of the hole enlargement treatment was extended from 2 hours to 20 hours.
实施例3： Example 3:
重复实施例1，只是将KOH改为KOH和K2CO3混合物（KOH与K2CO3的质量比为1:1）。 Repeat Example 1, but change the KOH to a mixture of KOH and K 2 CO 3 (the mass ratio of KOH to K 2 CO 3 is 1:1).
实施例4： Example 4:
重复实施例1，将氮气改为空气，处理时间2小时改为0.5小时。 Repeat Example 1, change the nitrogen into air, and change the treatment time from 2 hours to 0.5 hour.
实施例5： Example 5:
重复实施例1，将氮气改为氮气（70%）和CO2（30%）的混合气，处理时间2小时改为1小时。 Repeat Example 1, changing the nitrogen gas to a mixture of nitrogen (70%) and CO 2 (30%), and changing the treatment time from 2 hours to 1 hour.
对比例1： Comparative example 1:
取4g商业活性炭置于氩气中1850℃下处理1小时后，粉碎至12-16目，在200mL/min的氧气中于700℃处理0.5小时，冷却至室温即得到处理后的活性炭样品。 Take 4g of commercial activated carbon and place it in argon at 1850°C for 1 hour, crush it to 12-16 mesh, treat it in 200mL/min oxygen at 700°C for 0.5 hour, and cool it to room temperature to obtain the treated activated carbon sample.
对比例2： Comparative example 2:
重复对比例1，将氧气改为水蒸气，温度700℃改为500℃，处理时间0.5小时改为2小时。 Repeat Comparative Example 1, changing the oxygen to water vapor, changing the temperature from 700°C to 500°C, and changing the treatment time from 0.5 hours to 2 hours.
为了便于对比，未经过热处理的商业活性炭性质也一并列于表1。通过表1可以看出使用本发明提供的处理方法得到的活性炭微孔孔容与总孔容比值小、中孔率和大孔率大，所有实施例获得的活性炭样品微孔孔容与总孔容比值都不超过0.28。此外，通过实施例和对比例的对比可以看出，本发明提供的扩孔方法具有活性炭烧失率低的优点。 For comparison, the properties of commercial activated carbon without heat treatment are also listed in Table 1. As can be seen from Table 1, the micropore pore volume and total pore volume ratio of activated carbon obtained by the treatment method provided by the present invention is small, the mesopore rate and macroporosity are large, and the micropore pore volume and total pore volume of activated carbon samples obtained by all embodiments The volume ratio value does not exceed 0.28. In addition, it can be seen from the comparison of the examples and comparative examples that the pore-enlarging method provided by the present invention has the advantage of low loss-on-burn rate of activated carbon.
表1 不同处理方法得到的活性炭的性质 Table 1 Properties of activated carbon obtained by different treatment methods
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。 The above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.
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Cited By (17)
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| CN104014328A (en) * | 2014-06-20 | 2014-09-03 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | Carrier, residual oil hydrogenation catalyst based on carrier, and preparation method of carrier |
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| CN111977653A (en) * | 2020-08-24 | 2020-11-24 | 中国林业科学研究院林产化学工业研究所 | Modified activated carbon for super capacitor and preparation method thereof |
| CN113735302A (en) * | 2020-05-28 | 2021-12-03 | 宝山钢铁股份有限公司 | Method and device for removing SCOD (selective catalytic reduction) and total nitrogen in cold-rolling biochemical effluent |
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| CN101905154A (en) * | 2010-08-20 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | A method to improve the efficiency of visible-light-responsive doped M-TiO2/AC photocatalysts |
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| CN104014328A (en) * | 2014-06-20 | 2014-09-03 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | Carrier, residual oil hydrogenation catalyst based on carrier, and preparation method of carrier |
| CN104014328B (en) * | 2014-06-20 | 2016-08-10 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | A carrier, a residue hydrogenation catalyst based on the carrier and a preparation method thereof |
| CN104071786A (en) * | 2014-07-18 | 2014-10-01 | 福州大学 | Preparation method for graphitized activated carbon with high specific surface area |
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| CN110255558A (en) * | 2019-05-27 | 2019-09-20 | 榆林学院 | A method of active carbon is prepared using physical chemistry activation method |
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| CN113735302A (en) * | 2020-05-28 | 2021-12-03 | 宝山钢铁股份有限公司 | Method and device for removing SCOD (selective catalytic reduction) and total nitrogen in cold-rolling biochemical effluent |
| CN111977653A (en) * | 2020-08-24 | 2020-11-24 | 中国林业科学研究院林产化学工业研究所 | Modified activated carbon for super capacitor and preparation method thereof |
| CN111977653B (en) * | 2020-08-24 | 2023-06-02 | 中国林业科学研究院林产化学工业研究所 | Modified activated carbon for super capacitor and preparation method thereof |
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