CN111974450B - 一种粉煤灰基催化裂解催化剂及其制备方法 - Google Patents
一种粉煤灰基催化裂解催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 239000010881 fly ash Substances 0.000 title claims abstract description 30
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011324 bead Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 230000005284 excitation Effects 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 229910052596 spinel Inorganic materials 0.000 abstract description 3
- 239000011029 spinel Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 239000012075 bio-oil Substances 0.000 description 3
- 238000007233 catalytic pyrolysis Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000852 hydrogen donor Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
本发明公开了一种粉煤灰基催化裂解催化剂及其制备方法。主要包括如下步骤：1)将粉煤灰磁珠过50‑200目筛。2)将粉煤灰磁珠、含镁化合物和助剂按一定质量比混合置于等离子体球磨机，在激发电压5‑8kV下球磨0.5‑5h后得到催化剂。催化剂其表面碱性常数Kb和酸性常数Ka之比为1.2‑1.8：1，并具有0.4‑25nm孔径的多孔道结构。本发明以大宗固体废物粉煤灰为主要原料，通过高能等离子体球磨机制备铁镁尖晶石类材料作为生物质催化裂解的催化剂，具有制备工艺简单、催化效率高、易于大规模生产等优点，同时达到变废为宝的目的。
Description
技术领域
本发明属于生物质再利用技术领域，特别涉及一种粉煤灰基催化裂解催化剂及其制备方法。
背景技术
生物质快速催化热解制备高品质生物油技术，可实现化学品和液体燃料的制备，被认为是实现化石能源替代的有效途径之一。但是，生物油存在组分复杂、含氧量高、难分离等缺点，需经催化提质后才可作为替代燃料使用。为了提高生物油产率和目标产物选择性，生物质供氢热解技术应运而生。该技术通过引入氢气或供氢剂，为生物质热解反应体系提供足够的供氢体，稳定自由基碎片，从而获得稳定的热解产物。目前采用的供氢剂主要有四氢萘、小分子醇类、甲酸盐和有机高分子聚合物。氢气和醇类化合物价格昂贵，为生物质提供氢源的经济性较差。此外，氢气在高温高压下操作危险性较大，对设备要求也较高。除了加入一种氢量高的原料，催化剂载体也是重要的影响因素。微孔分子筛(如HZSM-5)因其规则的孔道结构、良好的水热稳定性、适宜的酸性和理想的择形催化选择性等优点，成为催化快速热裂解制备芳烃理想的催化剂。但是由于微孔分子筛单一的微孔结构导致在反应过程中传质阻力过大，不仅限制了反应速率和活性位的有效利用，还增加了反应过程中的积碳。因此，如何强化生物质催化热裂解反应过程中的传质，减少催化过程中的积碳，提高催化剂活性成为生物质催化热解的关键。
发明内容
本发明的第一个目的在于克服现有技术的不足，提供一种粉煤灰基催化裂解催化剂的制备方法。
一种粉煤灰基催化裂解催化剂的制备方法具体是：
1)将粉煤灰磁珠过50-200目筛；
2)将过筛后的粉煤灰磁珠、含镁化合物和助剂按一定质量比混合置于等离子体球磨机，在激发电压5-8kV下球磨0.5-5h后得到催化剂。
所述的含镁化合物包括氢氧化镁、碱式碳酸镁、碳酸镁、氧化镁、氯化镁、硫酸镁中的一种或几种。
所述的助剂为聚乙二醇、二甲基甲酰胺、戊醇、均三甲苯中的一种或几种。
所述的粉煤灰磁珠、含镁化合物和助剂的质量比为1：0.1-0.5：0.05-0.3。
本发明的第二个目的是提供一种粉煤灰基催化裂解催化剂，采用上述方法制备得到。
所述的催化剂其表面碱性常数Kb和酸性常数Ka之比为1.2-1.8：1，具有0.4-25nm孔径的多孔道结构。
本发明以大宗固体废物粉煤灰为主要原料，通过高能等离子体球磨机制备铁镁尖晶石类材料作为生物质催化裂解的催化剂。制备的铁镁尖晶石类材料具有0.4-25nm孔径的多孔道结构，表面碱性常数Kb和酸性常数Ka之比为1.2-1.8：1，酸碱性适宜，催化反应过程中传质阻力小，生物质大分子可进入催化剂孔道被定向裁剪，因此对于单环芳烃具有很好的选择性，克服了传统沸石分子筛制备工艺复杂、催化性能低等缺点。
具体实施方式
本发明结合以下实例作进一步的说明，但本发明的内容不仅限于实施例中所涉及的内容。
实施例1：
1)将粉煤灰磁珠过50目筛。
2)将100g粉煤灰磁珠、10g氧化镁和5g聚乙二醇按质量比1：0.1：0.05混合置于等离子体球磨机，在激发电压5kV下球磨5h后得到催化剂。催化剂表面碱性常数Kb和酸性常数Ka之比为1.2：1，具有0.4-10nm孔径的多孔道结构。
3)称量3g玉米芯和1.5g上述催化剂，然后将混合物料在450℃、氮气氛围下热解。通过气相色谱质谱分析，单环芳烃含量达到71％。
实施例2：
1)将粉煤灰磁珠过200目筛。
2)将100g粉煤灰磁珠、50g氯化镁和30g二甲基甲酰胺按质量比1：0.5：0.3混合置于等离子体球磨机，在激发电压8kV下球磨0.5h后得到催化剂。催化剂表面碱性常数Kb和酸性常数Ka之比为1.8：1，具有10-25nm孔径的多孔道结构。
3)称量4g木屑和2g上述催化剂，然后将混合物料在550℃、氮气氛围下热解。通过气相色谱质谱分析，单环芳烃含量达到75％。
实施例3：
1)将粉煤灰磁珠过100目筛。
2)将100g粉煤灰磁珠、20g氢氧化镁和10g戊醇按质量比1：0.2：0.1混合置于等离子体球磨机，在激发电压6kV下球磨4h后得到催化剂。催化剂表面碱性常数Kb和酸性常数Ka之比为1.5：1，具有0.8-20nm孔径的多孔道结构。
3)称量5g稻壳和2.5g上述催化剂，然后将混合物料在550℃、氮气氛围下热解。通过气相色谱质谱分析，单环芳烃含量为70％。
实施例4：
1)将粉煤灰磁珠过150目筛。
2)将100g粉煤灰磁珠、20g含镁化合物(即10g氧化镁、10g碳酸镁)和15g均三甲苯按质量比1：0.2：0.15混合置于等离子体球磨机，在激发电压7kV下球磨3h后得到催化剂。催化剂表面碱性常数Kb和酸性常数Ka之比为1.6：1，具有15-25nm孔径的多孔道结构。
3)称量6g麦秸和3g上述催化剂，然后将混合物料在650℃、氮气氛围下热解。通过气相色谱质谱分析，单环芳烃含量为76％。
实施例5：
1)将粉煤灰磁珠过200目筛。
2)将100g粉煤灰磁珠、40g含镁化合物(即20g碱式碳酸镁、20g硫酸镁)和15g聚乙二醇按质量比1：0.4：0.15混合置于等离子体球磨机，在激发电压6kV下球磨4h后得到催化剂。催化剂表面碱性常数Kb和酸性常数Ka之比为1.7：1，具有0.8-16nm孔径的多孔道结构。
3)称量8g麦秸和稻壳与4g上述催化剂，然后将混合物料在500℃、氮气氛围下热解。通过气相色谱质谱分析，单环芳烃含量为79％。
上述实施例并非是对于本发明的限制，本发明并非仅限于上述实施例，只要符合本发明要求，均属于本发明的保护范围。
Claims (4)
1.一种粉煤灰基催化裂解催化剂的制备方法，催化剂其表面碱性常数Kb和酸性常数Ka之比为1.2-1.8：1，具有0.4-25nm孔径的多孔道结构；其特征在于具体是：
1)将粉煤灰磁珠过50-200目筛；
2)将过筛后的粉煤灰磁珠、含镁化合物和助剂混合置于等离子体球磨机，在激发电压5-8kV下球磨0.5-5h后得到催化剂；其中所述的粉煤灰磁珠、含镁化合物和助剂的质量比为1：0.1-0.5：0.05-0.3。
2.根据权利要求1所述的一种粉煤灰基催化裂解催化剂的制备方法，其特征在于所述的含镁化合物包括氢氧化镁、碱式碳酸镁、碳酸镁、氧化镁、氯化镁、硫酸镁中的一种或几种。
3.根据权利要求1或2所述的一种粉煤灰基催化裂解催化剂的制备方法，其特征在于所述的助剂为聚乙二醇、二甲基甲酰胺、戊醇、均三甲苯中的一种或几种。
4.一种粉煤灰基催化裂解催化剂，其表面碱性常数Kb和酸性常数Ka之比为1.2-1.8：1，具有0.4-25nm孔径的多孔道结构，根据权利要求1-3任一项所述的方法制备得到。
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