CN103464099B - 一种变压吸附分离co2用活性炭的制备方法 - Google Patents
一种变压吸附分离co2用活性炭的制备方法 Download PDFInfo
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- CN103464099B CN103464099B CN201310371883.2A CN201310371883A CN103464099B CN 103464099 B CN103464099 B CN 103464099B CN 201310371883 A CN201310371883 A CN 201310371883A CN 103464099 B CN103464099 B CN 103464099B
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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 238000000926 separation method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002817 coal dust Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000004898 kneading Methods 0.000 claims abstract description 13
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- 239000003463 adsorbent Substances 0.000 claims abstract description 10
- 229940108066 Coal Tar Drugs 0.000 claims abstract description 9
- 239000011280 coal tar Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound 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[O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 239000002803 fossil fuel Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound 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[Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
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Classifications
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
本发明涉及一种变压吸附分离CO2用活性炭的制备方法,该方法是将煤粉与煤焦油、水、复合催化剂经混捏、成型、炭化、活化后得到柱状活性炭吸附剂。本发明以流量为0.9-1.2吨/小时的蒸汽进行活化,这种高速的蒸汽将炭化过程产生并积蓄在活性炭孔隙结构中的焦油物质及裂解产物清除,使活性炭封闭的孔能够打开,同时,在以硝酸盐和氯化物配伍的混合物复合催化剂的作用下,进一步分解官能团,改善活性炭微孔分布,从而提高活性炭的孔容和比表面积。采用本发明制备的活性炭,对CO2的吸附量0℃,1atm时可达到76ml/g以上;堆积密度620~640g/l;机械强度高,大于96%。
Description
技术领域
[0001] 本发明涉及一种活性炭的制备方法,具体地说,是一种变压吸附分离0)2用活性炭的制备方法。
背景技术
[0002] CO2是全球最重要的温室气体,其对温室效应的贡献占全部温室气体的50%,是造成气候变暖的主要原因。化石燃料燃烧及工业企业废气排放是CO2排放的主要来源。0)2也是一种重要的资源,在化工合成方面可以用于生产纯碱、合成尿素、碳酸氢铵等。对化石燃料燃烧排放气及工业企业废气中的0)2气体进行回收利用,可有效改善能源结构、减少温室气体排放。
[0003] 变压吸附技术是一种常用的分离和提纯工艺。变压吸附分离0)2是基于固态吸附剂对原料气中的CO2有选择性吸附作用,高压时吸附量较大,降压后被解吸出来。近十几年来广泛应用在脱除CO2I艺中。CO2常用的吸附剂为活性炭。活性炭的品种繁多,因原料及制造工艺条件差异,吸附性能也有较大差异。优化变压吸附过程首先要选用吸附量大、解吸性能好、分离系数大、机械强度高等性能优良的吸附剂。
发明内容
[0004] 本发明的目的就在于提供一种吸附量大、解吸性能好、分离系数大、机械强度高的变压吸附分离0)2用活性炭的制备方法。
[0005] 本发明的技术方案为:
[0006] —种变压吸附分离CO2用活性炭的制备方法,其特征是:将煤粉与煤焦油、水、复合催化剂经混捏、成型、炭化、活化后得到柱状活性炭吸附剂;
[0007] 所述煤焦油用量为煤粉重量的35-40%,水用量为煤粉重量的2-4%,复合催化剂用量为煤粉重量的2-3%,其中所述的复合催化剂是由25%~35%的硝酸盐和65~75%的氯化物组成,以重量百分比计。
[0008] 所述煤粉的粒度为170-200目。
[0009] 所述混捏是指在70-90 °C下搅拌15-20分钟。
[0010] 所述成型为将拌好的煤膏加入成型压力机内压制成直径2.3±0.2mm,高3_5mm的圆柱体炭条,自然瞭干。
[0011] 所述炭化为将炭条匀速投入旋转的炭化炉,以0.5m/min匀速从炉尾旋转至炉头出料,控制炉尾温度180-260°C,炉中温度400-480°C,炉头温度580_650°C。
[0012] 所述活化是指在蒸汽流量为0.9-1.2吨/小时,炉压为70-90Pa,温度850-930°C条件下活化24-26小时。
[0013] 本发明以流量为0.9-1.2吨/小时的蒸汽进行活化,这种高速的蒸汽将炭化过程产生并积蓄在活性炭孔隙结构中的焦油物质及裂解产物清除,使活性炭封闭的孔能够打开,同时,在以硝酸盐和氯化物配伍的混合物复合催化剂的作用下,进一步分解官能团,改善活性炭微孔分布,从而提高活性炭的孔容和比表面积。采用本发明制备的活性炭,对CO2的吸附量0°C,Iatm时可达到76ml/g以上;堆积密度620~640g/l ;机械强度高,大于96%。
具体实施方式
[0014] 实施例1
[0015] 将煤粉碎筛分到170目,倒入捏合锅(NH1500)内搅拌,捏合锅的温度在80~85°C之间,加入煤焦油(重量为煤粉重的35%)、水(重量为煤粉重的3%)、复合催化剂(重量为煤粉重的2%,其中硝酸盐占复合催化剂的30%,氯化物占复合催化剂的70%),搅拌15分钟。将拌好的煤膏加入成型压力机内压制成直径2.3±0.2mm,高3-5mm的圆柱体炭条,瞭干。将自然瞭干的炭条勾速投入旋转的炭化炉,利用倾斜重力原理,炭条以0.5m/min勾速从炉尾旋转至炉头出料,炉尾温度180-260 °C,炉中温度400-450 °C,炉头温度580-600 °C,经过加热干馏出炉冷却形成炭化料。
[0016] 将炭化料加入斯列普活化炉,水蒸气压力在0.2MPa-0.3MPa,蒸汽流量为0.9-1.0吨/小时,炉压70-80Pa,在温度为900°C的条件下活化24小时后得到柱状活性炭吸附剂。其0°C,Iatm时,CO2吸附量可达76.8ml/g,堆积密度628g/l,强度96.5%。
[0017] 实施例2
[0018] 将煤粉碎筛分到180目,倒入捏合锅(NH1500)内搅拌,捏合锅的温度在80~85°C之间,加入煤焦油(重量为煤粉重的38%)、水(重量为煤粉重的3%)、复合催化剂(重量为煤粉重的2%,其中硝酸盐占复合催化剂的25%,氯化物占复合催化剂的75%),搅拌15分钟。将拌好的煤膏加入成型压力机内压制成直径2.3±0.2mm,高3-5mm的圆柱体炭条,瞭干。将自然瞭干的炭条勾速投入旋转的炭化炉,利用倾斜重力原理,炭条以0.5m/min勾速从炉尾旋转至炉头出料,炉尾温度200-260°C,炉中温度450-480°C,炉头温度600_650°C。
[0019] 将炭化料加入斯列普活化炉,水蒸气压力在0.2MPa-0.3 MPa,蒸汽流量为0.9-1.0吨/小时,炉压80-90Pa,在温度为850°C的条件下活化26小时后得到柱状活性炭吸附剂。其0°C,Iatm时,CO2吸附量可达69.2ml/g,堆积密度630g/l,强度大于96.3%。
[0020] 实施例3
[0021] 将煤粉碎筛分到200目,倒入捏合锅(NH1500)内搅拌,捏合锅的温度在85~90°C之间,加入煤焦油(重量为煤粉重的40%)、水(重量为煤粉重的4%)、复合催化剂(重量为煤粉重的3%,其中硝酸盐占复合催化剂的35%,氯化物占复合催化剂的65%),搅拌20分钟。将拌好的煤膏加入成型压力机内压制成直径2.3±0.2mm,高3-5mm的圆柱体炭条,瞭干。将自然瞭干的炭条勾速投入旋转的炭化炉,利用倾斜重力原理,炭条以0.5m/min勾速从炉尾旋转至炉头出料,炉尾温度180-200°C,炉中温度400-450°C,炉头温度580_610°C。
[0022] 将炭化料加入斯列普活化炉,水蒸气压力在0.2MPa-0.3 MPa以上,蒸汽流量为
0.9-1.0吨/小时,炉压80-90Pa,在温度为930°C的条件下活化24小时后得到柱状活性炭吸附剂。其O0C,Iatm时,CO2吸附量可达61.8ml/g,堆积密度665g/l,强度96.5%。
[0023] 实施例4
[0024] 将煤粉碎筛分到170目,倒入捏合锅(NH1500)内搅拌,捏合锅的温度在80~85°C之间,加入煤焦油(重量为煤粉重的35%)、水(重量为煤粉重的3%)、复合催化剂(重量为煤粉重的2%,其中硝酸盐占复合催化剂的30%,氯化物占复合催化剂的70%),搅拌15-20分钟。将拌好的煤膏加入成型压力机内压制成直径2.3±0.2mm,高3_5mm的圆柱体炭条,瞭干。将自然瞭干的炭条勾速投入旋转的炭化炉,利用倾斜重力原理,炭条以0.5m/min勾速从炉尾旋转至炉头出料,炉尾温度180-260°C,炉中温度450-480°C,炉头温度630_650°C。
[0025] 将炭化料加入斯列普活化炉,水蒸气压力在0.2-0.3MPa,蒸汽流量为0.9-1.0吨/小时,炉压75-85Pa,在温度为930°C的条件下活化28小时后得到柱状活性炭吸附剂。其O0C,Iatm时,CO2吸附量可达75.4ml/g,堆积密度592g/l,强度96.7%。
Claims (4)
1.一种变压吸附分离CO2用活性炭的制备方法,其特征是:将煤粉与煤焦油、水、复合催化剂经混捏、成型、炭化、活化后得到柱状活性炭吸附剂; 所述煤焦油用量为煤粉重量的35-40%,水用量为煤粉重量的2-4%,复合催化剂用量为煤粉重量的2-3%,其中所述的复合催化剂是由25%~35%的硝酸盐和65~75%的氯化物组成,以重量百分比计; 所述炭化为将炭条勾速投入旋转的炭化炉,以0.5m/min勾速从炉尾旋转至炉头出料,控制炉尾温度180-260°C,炉中温度400-480°C,炉头温度580_650°C ; 所述活化是指在蒸汽流量为0.9-1.2吨/小时,炉压为70-90Pa,温度850_930°C条件下活化24-26小时。
2.按照权利要求1所述的变压吸附分离CO2用活性炭的制备方法,其特征是:所述煤粉的粒度为170-200目。
3.按照权利要求1所述的变压吸附分离CO2用活性炭的制备方法,其特征是:所述混捏是指在70-90 °C下搅拌15-20分钟。
4.按照权利要求1所述的变压吸附分离CO2用活性炭的制备方法,其特征是:所述成型为将拌好的煤膏加入成型压力机内压制成直径2.3±0.2_,高3-5_的圆柱体炭条,自然晾干。
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