CN108654702A - 一种劣质重油裂解脱硫减粘的催化剂、制备方法及其应用 - Google Patents
一种劣质重油裂解脱硫减粘的催化剂、制备方法及其应用 Download PDFInfo
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- CN108654702A CN108654702A CN201810272830.8A CN201810272830A CN108654702A CN 108654702 A CN108654702 A CN 108654702A CN 201810272830 A CN201810272830 A CN 201810272830A CN 108654702 A CN108654702 A CN 108654702A
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- catalyst
- heavy oil
- oil
- temperature
- visbreaking
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 14
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005336 cracking Methods 0.000 title claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000003921 oil Substances 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
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- 238000012360 testing method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
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- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 101710169849 Catalase isozyme A Proteins 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical class [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
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- -1 sulphur nitrogen oxygen carbon arsenic Chemical compound 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
本发明公开了一种劣质重油裂解脱硫减粘的催化剂、制备方法及其应用,属于绿色环保资源循环利用的技术领域。将所述的催化剂通过将废弃的FCC催化剂高温焙烧处理,脱除其中所含的硫、氮、氧、碳、砷有害杂质,获得具有一定孔容、孔径分布和比表面积的产物作为催化剂载体,以镍、钼、钴、钨或其组合作为活性组分,以氟、磷、硼等非金属酸性元素中的至少一种为助剂;将所述催化剂与劣质重油在临氢或非临氢的条件下进行裂解、脱硫、降凝、减粘,用于生产高附加值的油气产品。本发明制备的催化剂活性、选择性良好,轻质油气收率高,具有良好的社会经济效益和工业应用前景。
Description
技术领域
本发明涉及一种劣质重油裂解脱硫减粘的催化剂、制备方法和应用,属于绿色环保资源循环利用技术领域。
背景技术
随着原油的重质化和劣质化,原油中的胶质、沥青质、残炭、硫化物、氮化物、氧化物,有害的重金属铁、镍、钒、砷、等含量相应增加,特别是很多炼油企业为了提高效益,增加重油、渣油进催化裂化、催化裂解装置的进料比例,使得催化剂的中毒积碳增加、补充新剂、排出旧剂的速度和剂量相应增加。通常因各个企业进料性质和加工工艺不尽相同,催化剂的排出量也不相同,基本为装置进料量的1‰左右,对于年处理量为300-500万吨的催化装置,废FCC催化剂的排出量约为3000-5000吨。我国炼油大中型催化装置有200多套,每年排出的废弃的FCC催化剂相当可观,总量超过10万吨。排出的这些废FCC催化剂含有大量的碳化物、硫化物、氮化物、氧化物、及其铁、镍、钒、砷的化合物等有害杂质,如果不经处理,直接填埋或使用,会对环境造成很大的危害。这些废FCC催化剂经过处理,主要成分是由白土、U-Y分子筛、稀土组成,具有很大的有利用价值,可以变废为宝、化害为利。
过去很多企业对于废弃的FCC催化剂基本不回收利用,或是作为固体废物直接填埋,或是交固废公司作为废物处理,造成极大的浪费或污染。
发明内容
为了解决催化装置废催化剂的回收利用问题,本发明提供了一种劣质重油裂解脱硫减粘的催化剂、制备方法和应用。
本发明的技术方案是:
一种劣质重油裂解脱硫减粘的催化剂,所述的催化剂通过将废弃的FCC催化剂高温焙烧处理,脱除其中所含的硫、氮、氧、碳、砷等有害杂质,获得具有一定孔容、孔径分布和比表面积的产物作为催化剂载体,以镍、钼、钴、钨或其组合作为活性组分,以氟、磷、硼等非金属酸性元素中的至少一种为助剂。
上述劣质重油裂解脱硫减粘的催化剂的制备方法,包括如下步骤:
第一步,催化剂载体的制备
将废弃的FCC催化剂,经过高温焙烧处理,脱除废催化剂中所含的硫、氮、氧、碳、砷有害杂质,获得一定的孔容、孔径分布和比表面积的催化剂载体,其中,高温焙烧处理是在含氧的氧化反应条件下,在温度200-1000℃进行焙烧处理,优选焙烧温度为 300-800℃,进一步优选为400-600℃,焙烧时间为2-60小时,优选6-24小时,含氧的介质可以是空气、O2、CO2、H2O,O2+N2、优选空气加水;
第二步,催化剂的制备
将可溶性的镍盐、钼盐、钴盐、钨盐或其组合作为活性组分,加入助剂如可溶性的氟化物、磷化物、硼化物等非金属酸性元素和/或可溶性的钾盐、钠盐、钙盐、镁盐、锌盐、等碱性金属元素之中的至少一种配制成溶液;将催化剂载体浸渍于上述溶液中,在常压的条件下,进行浸渍、干燥、焙烧、冷却,得到所述催化剂,其中,浸渍的温度为室温-90℃,优选20-60℃,浸渍的时间是4-24小时;干燥的温度为60-200℃,优选 80-160℃,干燥的时间是4-24小时;焙烧的温度为200-800℃,优选300-600℃,焙烧的时间是4-24小时。
进一步的,第一步中,制得的催化剂载体的比表面积为50~500m2/g,孔容为0.2~1.0cm3/g,最几孔径分布为10-100nm。
进一步的,第二步中,活性组分与催化剂载体的质量比为2wt%-30wt%,优选5wt%~ 20wt%;助剂与催化剂载体的质量比为0.1wt%~10wt%,优选0.2wt%-5wt%。
上述催化剂的应用,将所述的催化剂与劣质重油一起加入反应器,在临氢或非临氢的条件下,进行裂解、异构、脱硫、降凝、减粘,反应生成的轻质油气通过冷凝、分馏,获得干气、液化气、汽油、煤油和柴油,重质馏分可作为低凝点低粘度的燃料油。
进一步的,本发明所述的劣质重油组分为常压渣油、减压渣油、催化澄清油、脱沥青油、煤焦油和超稠油中的一种或多种。
进一步的,反应的工艺条件是反应温度为200-800℃,优选250-600℃,进一步优选是300-500℃,反应的压力(绝压)是0.01-20MPa,优选0.1-10MPa,进一步优选 0.1-6.0MPa,反应的时间是1-24小时,优选2-10小时,进一步优选是3-6小时。
进一步的,所述反应器可以采用流化床反应器、悬浮床反应器、沸腾床反应器、浆态床反应器、移动床反应器或其组合。
与现有技术相比,本发明的有益效果是:为炼油催化装置废弃的FCC催化剂的回收利用提供了一种绿色环保的方法,也为劣质重油进行裂解、异构、脱硫、降凝,减粘生产轻质油气产品提供一种价格低廉经济高效的催化剂和技术方案。具有显著的社会经济效益和良好的工业应用前景。
具体实施方式
本发明将废FCC催化剂经过高温焙烧,脱除硫氮氧碳砷等元素的有害杂质后,其主要成分是由白土、U-Y分子筛和少量金属稀土等组成,具有适宜的比表面积、孔容和孔径分布,作为改性催化剂的载体;通过对催化剂载体负载活性组分,镍、钼、钴、钨或其组合,添加少量的助剂调节其酸碱性,如氟、磷、硼等酸性元素,钾、钠、钙镁、锌等碱性元素,作为劣质重油在临氢或非临氢的条件下进行裂解、异构、脱硫、降凝、减粘,用于生产高附加值的油气产品,催化剂活性、选择性良好,轻质油气收率高,可达到60%-95%以上。具有良好的社会经济效益和工业应用前景。
实施例1
催化剂载体的制备
取催化裂化装置排出的废催化剂500克,置于焙烧炉中,以5℃的升温速度均匀升温至600℃,在通氧的条件下,恒定温度600℃20小时,均匀降温至室温。催化剂的颗粒尺寸小于150目,比表面积360m2/g,孔容0.45cm3/g,最几孔径分布10-60nm。催化剂外观白色粉末状。以此作为改性催化剂的载体ZT。
实施例2
改性钼-镍-磷催化剂的制备
称取催化剂载体ZT,150.0克,将硝酸镍、钼酸铵、磷酸溶解于无离子水中配制成混合水溶液,将其水溶液预热至60℃的条件下,加入载体浸渍,不断搅拌0.5小时,静置6小时,浸渍结束后升温至120℃进行干燥、恒温120℃干燥12小时结束;干燥结束后均匀升温至550℃,焙烧8小时,冷却至室温,制得改性催化剂CAT-A。催化剂中 MO3的含量为15.6wt%,NiO的含量为5.3wt%,P2O5的含量为3.2wt%.
实施例3
改性催化剂的临氢应用评价
催化剂的评价装置是1000ml的不锈钢釜式磁力密封搅拌装置,取催化剂CAT-A25克,重油480克,350℃-550℃馏分,凝点大于80℃,总硫含量8600ppmw,将催化剂和重油加入反应器中,密封试压合格后,用氮气置换反应系统3次,开始升温,升温速率为5℃/min,升温到150℃,开搅拌装置,转速为400rpm,向反应系统补氢至3.0MPa,继续均匀升温至420℃,控制反应压力5.0MPa,稳定4小时,冷却至60℃,降压至常压,取出反应产物,进行分馏,其中气体产物为2.6wt%,汽油馏分32.3wt%,柴油馏分48.6wt%, 重油馏分16.5wt%,汽油硫含量为56ppmw,柴油硫含量为236ppmw,重油组分硫含量为 1056ppmw,凝固点-2℃。
实施例4
改性催化剂的临氢应用评价
催化剂的评价装置是1000ml的不锈钢釜式磁力密封搅拌装置,取催化剂CAT-A25克,重油520克,350℃-550℃馏分,凝点大于80℃,总硫含量8600ppmw,将催化剂和重油加入反应器中,密封试压合格后,用氮气置换反应系统3次,开始升温,升温速率为5℃/min,升温到150℃,开搅拌装置,转速为400rpm,向反应系统补氢至3.0MPa,继续均匀升温至440℃,控制反应压力12.0MPa,稳定4小时,冷却至60℃,降压至常压,取出反应产物,进行分馏,其中气体产物为4.3wt%,汽油馏分35.3wt%,柴油馏分 56.6wt%,重油馏分3.8wt%,汽油硫含量为8ppmw,柴油硫含量为36ppmw,重油组分硫含量为543ppmw,凝固点-10℃。
实施例5
改性催化剂的非临氢应用评价
催化剂的评价装置是1000ml的不锈钢釜式磁力密封搅拌装置,取催化剂CAT-A25克,重油500克,350℃-550℃馏分,凝点大于80℃,总硫含量8600ppmw,将催化剂和重油加入反应器中,密封试压合格后,用氮气置换反应系统3次,开始升温,升温速率为5℃/min,升温到150℃,开搅拌装置,转速为400rpm,反应系统充氮不临氢,继续均匀升温至420℃,控制反应压力0.5MPa,稳定4小时,冷却至60℃,降压至常压,取出反应产物,进行分馏,其中气体产物为3.2wt%,汽油馏分26.2wt%,柴油馏分43.8wt%,重油馏分26.8wt%,汽油硫含量为432ppmw,柴油硫含量为869ppmw,重油组分硫含量为 3125ppmw,凝点2℃。
实施例6
改性催化剂的非临氢应用评价
催化剂的评价装置是1000ml的不锈钢釜式磁力密封搅拌装置,取催化剂CAT-A25克,重油512克,350℃-550℃馏分,凝点大于80℃,总硫含量8600ppmw,将催化剂和重油加入反应器中,密封试压合格后,用氮气置换反应系统3次,开始升温,升温速率为5℃/min,升温到150℃,开搅拌装置,转速为400rpm,反应系统充氮不临氢,继续均匀升温至380℃,控制反应压力0.5MPa,稳定4小时,冷却至60℃,降压至常压,取出反应产物,进行分馏,其中气体产物为1.2wt%,汽油馏分22.5wt%,柴油馏分32.4wt%,重油馏分43.9wt%,汽油硫含量为512ppmw,柴油硫含量为1251ppmw,重油组分硫含量为 4325ppmw,凝点15℃。
实施例7
无催化剂的非临氢应用评价
催化剂的评价装置是1000ml的不锈钢釜式磁力密封搅拌装置,重油496克,350℃-550℃馏分,凝点大于80℃,总硫含量8600ppmw,将重油加入反应器中,密封试压合格后,用氮气置换反应系统3次,开始升温,升温速率为5℃/min,升温到150℃,开搅拌装置,转速为400rpm,反应系统充氮不临氢,继续均匀升温至380℃,控制反应压力 0.5MPa,稳定4小时,冷却至60℃,降压至常压,取出反应产物,进行分馏,其中气体产物为0.2wt%,汽油馏分3.2wt%,柴油馏分6.3wt%,重油馏分90.3wt%,汽油硫含量为 831ppmw,柴油硫含量为1534ppmw,重油组分硫含量为6943ppmw,凝点42℃。
上述实施例仅为对发明所作的例证,而并非对本发明实施方式的限定。对于所属领域的技术人员,还可以根据需要做出多种不同形式的修改或变动。
上述实施例说明,将炼油催化装置废弃的FCC催化剂进行回收利用是可行的,本发明提供了一种绿色环保的废FCC催化剂回收利用方法,也为劣质重油进行裂解、脱硫、降凝生产轻质油气产品提供一种价格低廉经济有效的催化剂和技术方案。具有显著的社会经济效益和良好的工业应用前景。
Claims (8)
1.一种劣质重油裂解脱硫减粘的催化剂,其特征在于,所述的催化剂通过将废弃的FCC催化剂高温焙烧处理,脱除其中所含的硫、氮、氧、碳、砷有害杂质,获得具有一定孔容、孔径分布和比表面积的产物作为催化剂载体,以镍、钼、钴、钨或其组合作为活性组分,以氟、磷、硼等非金属酸性元素中的至少一种为助剂。
2.如权利要求1所述的催化剂,其特征在于,催化剂载体的比表面积为50~500m2/g,孔容为0.2~1.0cm3/g,最几孔径分布为10-100nm。
3.一种劣质重油裂解脱硫减粘的催化剂的制备方法,其特征在于,包括如下步骤:
第一步,催化剂载体的制备
将废弃的FCC催化剂,经过高温焙烧处理,脱除废催化剂中所含的硫、氮、氧、碳、砷有害杂质,获得催化剂载体,其中,高温焙烧处理是在含氧的氧化反应条件下,在温度200-1000℃进行焙烧处理,焙烧时间为2-60小时,含氧的介质可以是空气、O2、CO2、H2O,O2+N2;
第二步,催化剂的制备
将可溶性的镍盐、钼盐、钴盐、钨盐或其组合作为活性组分,加入助剂如可溶性的氟化物、磷化物、硼化物等非金属酸性元素和/或可溶性的钾盐、钠盐、钙盐、镁盐、锌盐碱性金属元素之中的至少一种配制成溶液;将催化剂载体浸渍于上述溶液中,在常压的条件下,进行浸渍、干燥、焙烧、冷却,得到所述催化剂,其中,浸渍的温度为室温-90℃,浸渍的时间是4-24小时;干燥的温度为60-200℃,干燥的时间是4-24小时;焙烧的温度为200-800℃,焙烧的时间是4-24小时。
4.如权利要求3所述的方法,其特征在于,第一步中,制得的催化剂载体的比表面积为50~500m2/g,孔容为0.2~1.0cm3/g,最几孔径分布为10-100nm。
5.如权利要求3所述的方法,其特征在于,第二步中,活性组分与催化剂载体的质量比为2wt%-30wt%;助剂与催化剂载体的质量比为0.1wt%~10wt%。
6.如权利要求1或2所述的催化剂的应用,其特征在于,将所述的催化剂与劣质重油一起加入反应器,在临氢或非临氢的条件下,进行裂解、异构、脱硫、降凝、减粘,反应生成的轻质油气通过冷凝、分馏,获得干气、液化气、汽油、煤油和柴油,重质馏分可作为低凝点低粘度的燃料油。
7.如权利要求6所述的应用,其特征在于,所述的劣质重油组分为常压渣油、减压渣油、催化澄清油、脱沥青油、煤焦油和超稠油中的一种或多种。
8.如权利要求6所述的应用,其特征在于,反应的工艺条件是:反应温度为200-800℃,反应的压力是0.01-20MPa,反应的时间是1-24小时。
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