CN109621935B - 微介孔铝酸钙催化剂的分步固相合成方法 - Google Patents
微介孔铝酸钙催化剂的分步固相合成方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 16
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
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Abstract
本发明提供微介孔铝酸钙催化剂的分步固相合成方法，将氧化钙基粉体和氧化铝基粉体按照化学计量12:2‑15用研磨混合均匀后，用粘合增孔剂粘接造粒，第一步在回转窑反应器中以反应温度300‑500℃、停留时间0.2‑3.5小时的条件热解生焦，第二步在内热式回转窑反应器中加热到出口温度900℃‑1500℃、停留时间0.1‑5小时的条件固相反应生成铝酸钙，第三步利用高温水蒸气气化铝酸钙中的热解焦造孔，得到微介孔铝酸钙催化剂。
Description
1.技术领域
本发明提供微介孔铝酸钙催化剂的分步固相合成方法，属于精细化工领域。
2.背景技术
劣质重油具有富含多环芳烃，碳氢比、粘度和密度大，硫、氮、氧、残碳、重金属和机械杂质含量过高，易缩合生焦等资源特性，对常规重油加工路线提出了巨大挑战，现有的重油加工技术大多难以满足高效清洁“化工型”加工的要求。延迟焦化是目前处理劣质重油的首选技术，但面临劣质高硫焦炭产量大、焦化蜡油收率低且“化工型”加工难度大、大量挥发物排放的环保压力和弹丸焦安全隐患等诸多挑战；催化裂化和加氢裂化技术用于劣质重油加工存在转化率、烯烃产品选择性差和收率低，催化剂失活快、消耗量过大，装置稳定性差和加工成本过高等难题；溶剂脱沥青技术用于劣质重油加工存在脱沥青油收率低且“化工型”加工难度大，硬沥青高效量大的利用途径成为其工业化瓶颈；重油悬浮床加氢技术理论上能够满足劣质重油高效清洁预处理的要求，但转化率低、氢耗过高、重金属脱除率低、尾油加工和廉价氢源亟待解决，工艺和设备匹配性还存在缺陷，目前尚无成功大规模工业应用，另外加氢蜡油需要二次加工才能实现“化工型”，且过程加氢脱氢往复循环造成能耗过高，经济效益差。
尽管近年来国内外开发了较多的重油催化裂解多产低碳烯烃新技术，如中石化石科院开发的DCC/CPP工艺、UOP公司开发的PetroFCC工艺、日本石油能源中心开发的HS-FCC工艺、THR工艺、德国有机化学研究所TCSC工艺、印度石油公司开发的INDMAX(UCC)工艺、Exxon mobil与Kellog公司联合开发的Maxofin工艺和中国石油学提出的两段提升管催化裂解(TMP)工艺等，受到业界的广泛关注和示范应用。但由于酸性分子筛类催化剂结构性能与重油大分子的适应匹配性要求，目前使用常压渣油、减压渣油和脱沥青油等劣质原料催化裂解制烯烃，孔道结构较小，较大的重油分子在传质过程中扩散受限，不易进入分子筛内部进行择形裂化，加之酸性分子筛较强的氢转移性能，烯烃的收率和选择性提高幅度受到限制；聚集在分子筛表面的分子在酸中心的作用下容易过度裂化，造成产品分布不良或者结焦缩合，从而堵塞催化剂孔道。目前现有的工业择型催化剂利用常压渣油、减压渣油、脱沥青油等劣质原料催化裂解制低碳烯烃，往往会带来催化剂中毒、雾化效果差、生焦量大及转化率和选择性大幅度降低等诸多问题。往往会存在催化剂中毒、雾化效果差、生焦量大及转化率和选择性大幅度降低等诸多问题，亟待进一步优化开发。
铝酸钙催化剂是由氧化钙基和氧化铝基粉体材料合成的碱性无机化合物，碱性强、硬度大、熔点高、耐磨性好，能够抗高温、耐水蒸气和重金属污染；无氢转移效应，能大幅度提高热解烯烃的选择性；较强的脱氢性能能使氢自由基抑制重油热解的芳烃类自由基发生缩聚反应，减少生焦，从而大幅度提高了重油裂化的液体收率；同时还可促进待生催化剂的结焦燃烧或气化再生反应，降低再生温度，是一个具有较大应用潜力的重油裂解和化工型加工的催化剂。但目前铝酸钙催化剂主要通过高温固相合成，孔隙结构欠缺，表面积小，比重大，难以最大化发挥其碱性催化剂抑制生焦、强化烯烃选择性的优势，成为铝酸钙催化剂工业化应用的瓶颈。
3.发明内容
本发明的目的就是为了克服现有铝酸钙催化剂制备技术存在的不足而提供微介孔铝酸钙催化剂的分步固相合成方法，通过氧化钙基粉体和氧化铝基粉体超细研磨混合、易生焦的粘合增孔剂造粒、低温段生焦占位、高温固相合成和水蒸气气化焦造孔或空气燃烧焦造孔等措施制取微介孔的大比表面积、低密度、高强度铝酸钙催化剂。
本发明的技术方案：
本发明提供微介孔铝酸钙催化剂的分步固相合成方法，其技术特征是将氧化钙基粉体和氧化铝基粉体按照化学计量12:2-15用研磨混合均匀后，用0.1-15％的粘合增孔剂粘接造粒成型，第一步在回转窑反应器中以出口反应温度300-500℃、停留时间0.2-3.5小时的条件热解生焦，第二步在内热式回转窑反应器中加热到出口温度900℃-1500℃、停留时间0.1-5小时的条件固相反应生成铝酸钙，第三步消解气化铝酸钙中热解焦造孔，得到微介孔铝酸钙催化剂。
氧化钙基粉体为纳米碳酸钙粉体、氢氧化钙粉体、氧化钙粉体、醋酸钙、硝酸钙、石灰石粉体中的单独一种粉体或两种以上的粉体混合物。
氧化铝基粉体为铝溶胶、氧化铝粉体、氢氧化铝粉体、铝酸钙粉体中的单独一种粉体或两种以上的粉体混合物。
研磨混合采用球磨机、胶体磨、雷蒙粉碎机、超细粉碎机、立式粉碎机、棒磨机中的一种。
粘合增孔剂为淀粉、改性淀粉、木质素粘合剂、纤维素粘合剂、煤焦油、油浆、液体沥青、沥青粉、聚乙二醇、酚醛树脂、脲醛树脂、聚乙烯醇缩甲醛树脂、聚乙烯醇缩乙醛树脂、碳粉、骨胶、聚醋酸乙烯树脂中的单独一种粉体或两种以上的粉体混合物。
粘合增孔剂粘接造粒成型为喷雾造粒或半干发混合造粒。
消解气化铝酸钙中的热解焦造孔为水蒸气高温气化造孔或空气燃烧造孔。
微介孔铝酸钙催化剂按要求粒度范围分级，得到合适的微介孔铝酸钙催化剂；过细或过粗的铝酸钙催化剂可返回到球磨机作为原料重新使用。
本发明将实施例来详细叙述本发明的特点。
5.具体实施方式
实施例1，将纳米碳酸钙粉体和铝溶胶按照氧化钙：氧化铝基化学计量12:7用球磨机研磨混合均匀、形成钙铝混合粉体，用2％的改性淀粉和沥青粉的混合物加入15％的水配成粘合剂熔液后加入到混料机中与钙铝混合粉体半干法混合粘接造粒成型；第一步在回转窑反应器中在出口反应温度500℃、停留时间2.5小时的条件使粘合剂热解生焦，第二步在内热式回转窑反应器中加热到出口温度1200℃、停留时间3.5小时的条件使碳酸钙分解、氧化钙和氧化铝发生固相反应生成铝酸钙微球粉，第三步在旋转窑出口设置的流化床气化器中用水蒸气气化铝酸钙中的热解焦造孔的同时也由于气化吸热反应降低了铝酸钙催化剂温度，流化的铝酸钙催化剂按要求粒度范围分级，得到合适的微介孔铝酸钙催化剂；过细或过粗的铝酸钙催化剂可返回到球磨机作为原料重新使用。
制备的微介孔铝酸钙催化剂比表面积由普通铝酸钙粉体的不到1m2/g提高到120m2/g，密度由4000kg/m3降到0.9kg/m3，微介孔孔容提高了80％。
实施例2，将石灰石粉体和氧化铝粉以及过细的铝酸钙粉体按照氧化钙：氧化铝基化学计量12:6用球磨机研磨混合均匀、形成钙铝混合粉体，用1％的粘合剂加入10％的水配成木质素粘合剂熔液后加入到混料机中与钙铝混合粉体半干法混合粘接造微粒；第一步在回转窑反应器中在出口反应温度500℃、停留时间3.5小时的条件使粘合剂热解生焦，第二步在内热式回转窑反应器中加热到出口温度1100℃、停留时间2.5小时的条件使石灰石分解、氧化钙和氧化铝发生固相反应生成铝酸钙微球，第三步在旋转窑出口设置的移动床燃烧器中用分段空气燃烧铝酸钙中的热解焦造孔同时进步促进铝酸钙晶相生成，铝酸钙催化剂按要求粒度范围分级，得到粒度范围合适的微介孔铝酸钙微球催化剂；过细或过粗的铝酸钙催化剂可返回到球磨机作为原料重新使用。
制备的微介孔铝酸钙催化剂比表面积由普通铝酸钙粉体的不到1m2/g提高到140m2/g，密度由4000kg/m3降到0.92kg/m3，微介孔孔容提高了60％。
实施例3，将纳米碳酸钙粉体和铝溶胶按照氧化钙：氧化铝基化学计量12:7，并加入1％的木质素粘合剂用胶体磨研磨混合均匀，形成钙铝混合浆体，雾化造粒成型；第一步在回转窑反应器中在出口反应温度450℃、停留时间1.5小时的条件使钙铝微粉中的粘合剂热解生焦，第二步在内热式回转窑反应器中加热到出口温度1200℃、停留时间3.5小时的条件使碳酸钙分解、氧化钙和氧化铝发生固相反应生成铝酸钙微球，第三步在旋转窑出口设置的流化床气化器中用水蒸气气化铝酸钙中的热解焦造孔的同时也由于气化吸热反应降低了铝酸钙催化剂温度，流化的铝酸钙催化剂按要求粒度范围分级，得到合适的微介孔铝酸钙催化剂；过细或过粗的铝酸钙催化剂可返回到胶体磨作为原料重新使用。
制备的微介孔铝酸钙催化剂比表面积由普通铝酸钙粉体的不到1m2/g提高到200m2/g，密度由4000kg/m3降到0.85kg/m3，微介孔孔容提高了90％。
本发明所提供的微介孔铝酸钙催化剂的分步固相合成方法，通过氧化钙基粉体和氧化铝基粉体超细研磨混合、易生焦的粘合增孔剂造粒成型、低温段生焦占位、高温固相合成和消解焦造孔等技术手段制取微介孔的大比表面积、低密度、高强度铝酸钙催化剂，催化剂耐磨指数小于0.3％，耐温最高可达850℃。
Claims (7)
1.微介孔铝酸钙催化剂的分步固相合成方法，其特征在于 将氧化钙基粉体和氧化铝基粉体按照化学计量12:2-15用研磨混合均匀后，用0.1-15％的粘合增孔剂粘接造粒成型，粘合增孔剂为淀粉、改性淀粉、木质素粘合剂、纤维素粘合剂、煤焦油、油浆、液体沥青、沥青粉、聚乙二醇、酚醛树脂、脲醛树脂、聚乙烯醇缩甲醛树脂、聚乙烯醇缩乙醛树脂、碳粉、骨胶、聚醋酸乙烯树脂中的单独一种粉体或两种以上的粉体混合物；第一步在回转窑反应器中以出口反应温度300-500℃、停留时间0.2-3.5小时的条件热解生焦，第二步在内热式回转窑反应器中加热到出口温度900℃-1500℃、停留时间0.1-5小时的条件固相反应生成铝酸钙，第三步消解气化铝酸钙中热解焦造孔，得到微介孔铝酸钙催化剂。
2.根据权利要求1所述的微介孔铝酸钙催化剂的分步固相合成方法，其特征在于氧化钙基粉体为纳米碳酸钙粉体、氢氧化钙粉体、氧化钙粉体、醋酸钙、硝酸钙、石灰石粉体中的单独一种粉体或两种以上的粉体混合物。
3.根据权利要求1所述的微介孔铝酸钙催化剂的分步固相合成方法，其特征在于氧化铝基粉体为铝溶胶、氧化铝粉体、氢氧化铝粉体、铝酸钙粉体中的单独一种粉体或两种以上的粉体混合物。
4.根据权利要求1所述的微介孔铝酸钙催化剂的分步固相合成方法，其特征在于研磨混合采用球磨机、胶体磨、雷蒙粉碎机、超细粉碎机、立式粉碎机、棒磨机中的一种。
5.根据权利要求1所述的微介孔铝酸钙催化剂的分步固相合成方法，其特征在于粘合增孔剂粘接造粒成型为喷雾造粒或半干发混合造粒。
6.根据权利要求1所述的微介孔铝酸钙催化剂的分步固相合成方法，其特征在于消解气化铝酸钙中的热解焦造孔为水蒸气高温气化造孔或空气燃烧造孔。
7.根据权利要求1所述的微介孔铝酸钙催化剂的分步固相合成方法，其特征在于微介孔铝酸钙催化剂按要求粒度范围分级，得到合适的微介孔铝酸钙催化剂；过细或过粗的铝酸钙催化剂可返回到球磨机作为原料重新使用。
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