CN112206815A - 一种用于润滑油异构化的催化剂及其制备方法 - Google Patents
一种用于润滑油异构化的催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 16
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 64
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 150000007530 organic bases Chemical class 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims abstract description 8
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- 239000000853 adhesive Substances 0.000 claims abstract description 7
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- 238000000034 method Methods 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
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- 239000011975 tartaric acid Substances 0.000 claims description 2
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- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
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- 239000002131 composite material Substances 0.000 abstract description 2
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- 241000219782 Sesbania Species 0.000 description 6
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000002283 diesel fuel Substances 0.000 description 1
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- 239000000295 fuel oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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Abstract
本发明涉及一种用于润滑油异构化的催化剂及其制备方法。所述催化剂由有机碱改性ZSM‑48分子筛、有机碱改性ZSM‑5分子筛、氧化石墨烯、活性金属组分、氧化铝、助挤剂、粘合剂组成。本发明催化剂含有有机碱改性的复合分子筛,可以大幅降低产物中的正构烷烃含量,同时使粘度指数有较大程度的提高,表明本发明催化剂具有加氢开环性能好、加氢异构化能力强的特点,可以用于加氢裂化石油炼制过程中中优质润滑油的生产。
Description
技术领域
本发明涉及催化剂技术领域,尤其涉及一种用于润滑油异构化的催化剂及其制备方法。
背景技术
加氢裂化技术具有原料适应性强、生产操作和产品方案灵活性大、产品质量好等特点,能够将各种重质劣质进料直接转化为市场急需的优质喷气燃料、柴油、润滑油基础料以及化工石脑油和尾油蒸汽裂解制乙烯原料,已成为现代炼油和石油化学工业最重要的重油深度加工工艺之一,在国内外获得日益广泛的应用。
润滑油基础油在成品润滑油中的含量通常为70%-99%,基础油的质量直接影响着润滑油的质量。我国润滑油的生产状况是低档产品产量过大,中高档产品比例偏小,高端产品缺口较大,而且,在质量方面与国际水平有较大差距。中高档产品比例偏小,高端产品缺口较大,而且在质量方面与国际水平有较大的差距。主要原因是能生产高档润滑油的基础油所占比例偏低,开发某些高档润滑油产品所需的低粘度、低凝、高粘度指数或超高粘度指数基础油尚不能生产。因此,亟需一种能够制备高质量润滑油基础油的方法。
综上所述,本领域缺乏满足上述技术要求的一种用于润滑油异构化的催化剂及其制备方法。
发明内容
本发明的目的在于提供一种用于润滑油异构化的催化剂及其制备方法。
为实现上述目的,本发明提供一种用于润滑油异构化的催化剂,所述催化剂由有机碱改性ZSM-48分子筛、有机碱改性ZSM-5分子筛、氧化石墨烯、活性金属组分、氧化铝、助挤剂、粘合剂组成。
优选地,所述催化剂由以下重量百分比的原料组成:20~25%wt有机碱改性ZSM-48分子筛、10~15%wt有机碱改性ZSM-5分子筛、2~3%wt石墨烯、16~20%wt活性金属组分(以单质计)、9~10%wt助挤剂、5~7%wt粘合剂、余量为氧化铝。
优选地,所述氧化石墨烯为环氧氯丙烷改性的氧化石墨烯。
优选地,所述活性金属组分包括VIB族金属或VIII族金属中的一种或两种以上的组合。
优选地,所述活性金属组分为镍、钨、钯、铂。
优选地,所述有机碱改性ZSM-5分子筛的制备方法为:将ZSM-5分子筛加入到装有有机碱溶液的耐压容器中,并将***密闭,升压至0.6~1.0MPa,然后升温至90~100℃,恒温处理10~14小时,取出洗涤干燥后,在450~650℃条件下焙烧6~8小时,得到有机碱改性ZSM-5分子筛;所述有机碱溶液的浓度为0.65~1.0mol/L;所述ZSM-5分子筛的加入量(g)与有机碱溶液体积(ml)的比例1:5~10。
优选地,所述有机碱改性ZSM-48分子筛的制备方法为:将ZSM-48分子筛加入到装有有机碱溶液的耐压容器中,并将***密闭,升压至0.8~1.2MPa,然后升温至140~150℃,恒温处理8~10小时,取出洗涤干燥后,在650~750℃条件下焙烧6~8小时,得到有机碱改性ZSM-48分子筛;所述有机碱溶液的浓度为1.35~2.0mol/L;所述ZSM-48分子筛的加入量(g)与有机碱溶液体积(ml)的比例1:8~12。
优选地,所述有机碱选自四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵中的一种或两种以上组合。
优选地,所述助挤剂选自淀粉、田菁粉、羟乙基甲基纤维素、甲基纤维素、聚乙二醇中的一种或两种以上的组合。
优选地,所述粘合剂为含有硝酸、柠檬酸、乙二酸、酒石酸中的一种或两种以上的组合的酸溶液。
优选地,所述酸溶液为含有0.4%硝酸的溶液。
本发明还提供一种用于润滑油异构化的催化剂的制备方法,所述方法包括如下步骤:
(1)将氧化铝粉、有机碱改性ZSM-48分子筛粉末、有机碱改性ZSM-5分子筛粉末、石墨烯粉混合均匀,然后加入助挤剂、粘合剂,充分碾压后成型,然后在550~650℃焙烧10~14小时,得到催化剂载体;
(2)用含有两种活性金属组分的溶液等体积浸渍步骤(1)得到的催化剂载体4~6小时,然后在100~120℃干燥12~16小时、650~750℃焙烧10~14小时,得催化剂中间体;
(3)用含有另外两种活性金属组分的溶液等体积浸渍步骤(2)得到的催化剂中间体4~6小时,然后在100~120℃干燥12~16小时、650~750℃焙烧10~14小时,即得。
与现有技术相比,本发明具有如下有益效果:
1.本发明催化剂含有有机碱改性的复合分子筛,可以大幅降低产物中的正构烷烃含量,同时使粘度指数有较大程度的提高,表明本发明催化剂具有加氢开环性能好、加氢异构化能力强的特点,可以用于加氢裂化石油炼制过程中中优质润滑油的生产。
2.本发明的制备方法、操作方便,易于大规模生产,且质量稳定。
3.本发明原材料在国内充足,价格适宜,使其规模化生产没有太高的成本限制。
具体实施方式
实施例1
各原料的用量见表1。
(1)将氧化铝粉、有机碱改性ZSM-48分子筛粉末、有机碱改性ZSM-5分子筛粉末、氧化石墨烯粉混合均匀,然后加入羟乙基甲基纤维素、田菁粉、0.4%硝酸溶液,充分碾压后成型,然后在550℃焙烧14小时,得到催化剂载体;
(2)用含有镍、钯的溶液等体积浸渍步骤(1)得到的催化剂载体4小时,然后在100℃干燥16小时、650℃焙烧14小时,得催化剂中间体;
(3)用含有铂、钨的溶液等体积浸渍步骤(2)得到的催化剂中间体4小时,然后在100℃干燥16小时、650℃焙烧14小时,即得。
有机碱改性ZSM-48分子筛的制备:以1:8(g:ml)的比例将ZSM-48分子筛加入到装有四丁基氢氧化铵溶液(1.35mol/L)的耐压容器中,并将***密闭,升压至0.8MPa,然后升温至140℃,恒温处理10小时,取出洗涤干燥后,在650℃条件下焙烧8小时,得到有机碱改性ZSM-48分子筛。
有机碱改性ZSM-5分子筛的制备:以1:5(g:ml)的比例将ZSM-5分子筛加入到装有四甲基氢氧化铵溶液(1.0mol/L)的耐压容器中,并将***密闭,升压至1.0MPa,然后升温至100℃,恒温处理14小时,取出洗涤干燥后,在650℃条件下焙烧6小时,得到有机碱改性ZSM-5分子筛。
实施例2
各原料的用量见表1。
(1)将氧化铝粉、有机碱改性ZSM-48分子筛粉末、有机碱改性ZSM-5分子筛粉末、氧化石墨烯粉混合均匀,然后加入羟乙基甲基纤维素、田菁粉、0.4%硝酸溶液,充分碾压后成型,然后在650℃焙烧10小时,得到催化剂载体;
(2)用含有镍、铂的溶液等体积浸渍步骤(1)得到的催化剂载体6小时,然后在120℃干燥12小时、750℃焙烧10小时,得催化剂中间体;
(3)用含有钯、钨的溶液等体积浸渍步骤(2)得到的催化剂中间体6小时,然后在120℃干燥12小时、750℃焙烧10小时,即得。
有机碱改性ZSM-48分子筛的制备:以1:10(g:ml)的比例将ZSM-48分子筛加入到装有四丁基氢氧化铵溶液(1.75mol/L)的耐压容器中,并将***密闭,升压至1.2MPa,然后升温至150℃,恒温处理8小时,取出洗涤干燥后,在750℃条件下焙烧6小时,得到有机碱改性ZSM-48分子筛。
有机碱改性ZSM-5分子筛的制备:以1:10(g:ml)的比例将ZSM-5分子筛加入到装有四乙基氢氧化铵溶液(0.65mol/L)的耐压容器中,并将***密闭,升压至0.6MPa,然后升温至90℃,恒温处理10小时,取出洗涤干燥后,在450℃条件下焙烧8小时,得到有机碱改性ZSM-5分子筛。
实施例3
各原料的用量见表1。
(1)将氧化铝粉、有机碱改性ZSM-48分子筛粉末、有机碱改性ZSM-5分子筛粉末、氧化石墨烯粉混合均匀,然后加入羟乙基甲基纤维素、田菁粉、0.4%硝酸溶液,充分碾压后成型,然后在600℃焙烧12小时,得到催化剂载体;
(2)用含有钯、钨的溶液等体积浸渍步骤(1)得到的催化剂载体5小时,然后在110℃干燥14小时、700℃焙烧12小时,得催化剂中间体;
(3)用含有镍、铂的溶液等体积浸渍步骤(2)得到的催化剂中间体5小时,然后在110℃干燥14小时、700℃焙烧12小时,即得。
有机碱改性ZSM-48分子筛的制备:以1:12(g:ml)的比例将ZSM-48分子筛加入到装有四丁基氢氧化铵溶液(2.0mol/L)的耐压容器中,并将***密闭,升压至1.2MPa,然后升温至150℃,恒温处理8小时,取出洗涤干燥后,在750℃条件下焙烧6小时,得到有机碱改性ZSM-48分子筛。
有机碱改性ZSM-5分子筛的制备:以1:8(g:ml)的比例将ZSM-5分子筛加入到装有四丙基氢氧化铵溶液(0.65mol/L)的耐压容器中,并将***密闭,升压至0.6MPa,然后升温至90℃,恒温处理10小时,取出洗涤干燥后,在450℃条件下焙烧8小时,得到有机碱改性ZSM-5分子筛。
对比例1
各原料的用量见表1。
(1)将氧化铝粉、普通ZSM-48分子筛粉末、有机碱改性ZSM-5分子筛粉末、氧化石墨烯粉混合均匀,然后加入羟乙基甲基纤维素、田菁粉、0.4%硝酸溶液,充分碾压后成型,然后在600℃焙烧12小时,得到催化剂载体;
(2)用含有钯、钨的溶液等体积浸渍步骤(1)得到的催化剂载体5小时,然后在110℃干燥14小时、700℃焙烧12小时,得催化剂中间体;
(3)用含有镍、铂的溶液等体积浸渍步骤(2)得到的催化剂中间体5小时,然后在110℃干燥14小时、700℃焙烧12小时,即得。
有机碱改性ZSM-5分子筛的制备:以1:8(g:ml)的比例将ZSM-5分子筛加入到装有四丙基氢氧化铵溶液(0.65mol/L)的耐压容器中,并将***密闭,升压至0.6MPa,然后升温至90℃,恒温处理10小时,取出洗涤干燥后,在450℃条件下焙烧8小时,得到有机碱改性ZSM-5分子筛。
对比例2
各原料的用量见表1。
(1)将氧化铝粉、有机碱改性ZSM-48分子筛粉末、普通ZSM-5分子筛粉末、氧化石墨烯粉混合均匀,然后加入羟乙基甲基纤维素、田菁粉、0.4%硝酸溶液,充分碾压后成型,然后在600℃焙烧12小时,得到催化剂载体;
(2)用含有钯、钨的溶液等体积浸渍步骤(1)得到的催化剂载体5小时,然后在110℃干燥14小时、700℃焙烧12小时,得催化剂中间体;
(3)用含有镍、铂的溶液等体积浸渍步骤(2)得到的催化剂中间体5小时,然后在110℃干燥14小时、700℃焙烧12小时,即得。
有机碱改性ZSM-48分子筛的制备:以1:12(g:ml)的比例将ZSM-48分子筛加入到装有四丁基氢氧化铵溶液(2.0mol/L)的耐压容器中,并将***密闭,升压至1.2MPa,然后升温至150℃,恒温处理8小时,取出洗涤干燥后,在750℃条件下焙烧6小时,得到有机碱改性ZSM-48分子筛。
表1
实施例4催化剂性能测试
采用200ml小型加氢装置进行,测试前对实施例1~3和对比例1、2的催化剂进行预硫化。测试条件为:压力17.8mpa,氢油体积比为500,空速为1.0h-1,转化率为80%。原料油先经过FF-46床层然后直接进入催化剂床层,经过FF-46床层时控制原料油中的有机氮含量低于15ppm。结果见表2。
表2催化剂性能测试结果
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式,并且很显然,根据上述教导,可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用,从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。
Claims (9)
1.一种用于润滑油异构化的催化剂,其特征在于,所述催化剂由以下重量百分比的原料组成:20~25%wt有机碱改性ZSM-48分子筛、10~15%wt有机碱改性ZSM-5分子筛、2~3%wt石墨烯、16~20%wt活性金属组分(以单质计)、9~10%wt助挤剂、5~7%wt粘合剂、余量为氧化铝。
2.根据权利要求1所述的催化剂,其特征在于,所述氧化石墨烯为环氧氯丙烷改性的氧化石墨烯。
3.根据权利要求1所述的催化剂,其特征在于,所述活性金属组分包括VIB族金属或VIII族金属中的一种或两种以上的组合。
4.根据权利要求3所述的催化剂,其特征在于,所述活性金属组分为镍、钨、钯、铂。
5.根据权利要求1所述的催化剂,其特征在于,所述有机碱改性ZSM-5分子筛的制备方法为:将ZSM-5分子筛加入到装有有机碱溶液的耐压容器中,并将***密闭,升压至0.6~1.0MPa,然后升温至90~100℃,恒温处理10~14小时,取出洗涤干燥后,在450~650℃条件下焙烧6~8小时,得到有机碱改性ZSM-5分子筛;所述有机碱溶液的浓度为0.65~1.0mol/L;所述ZSM-5分子筛的加入量(g)与有机碱溶液体积(ml)的比例1:5~10。
6.根据权利要求1所述的催化剂,其特征在于,所述有机碱改性ZSM-48分子筛的制备方法为:将ZSM-48分子筛加入到装有有机碱溶液的耐压容器中,并将***密闭,升压至0.8~1.2MPa,然后升温至140~150℃,恒温处理8~10小时,取出洗涤干燥后,在650~750℃条件下焙烧6~8小时,得到有机碱改性ZSM-48分子筛;所述有机碱溶液的浓度为1.35~2.0mol/L;所述ZSM-48分子筛的加入量(g)与有机碱溶液体积(ml)的比例1:8~12。
7.根据权利要求1所述的催化剂,其特征在于,所述有机碱选自四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵中的一种或两种以上组合。
8.根据权利要求1所述的催化剂,其特征在于,所述助挤剂选自淀粉、田菁粉、羟乙基甲基纤维素、甲基纤维素、聚乙二醇中的一种或两种以上的组合;所述粘合剂为含有硝酸、柠檬酸、乙二酸、酒石酸中的一种或两种以上的组合的酸溶液。
9.一种如权利要求1~8所述的用于润滑油异构化的催化剂的制备方法,其特征在于,所述方法包括如下步骤:
(1)将氧化铝粉、有机碱改性ZSM-48分子筛粉末、有机碱改性ZSM-5分子筛粉末、石墨烯粉混合均匀,然后加入助挤剂、粘合剂,充分碾压后成型,然后在550~650℃焙烧10~14小时,得到催化剂载体;
(2)用含有两种活性金属组分的溶液等体积浸渍步骤(1)得到的催化剂载体4~6小时,然后在100~120℃干燥12~16小时、650~750℃焙烧10~14小时,得催化剂中间体;
(3)用含有另外两种活性金属组分的溶液等体积浸渍步骤(2)得到的催化剂中间体4~6小时,然后在100~120℃干燥12~16小时、650~750℃焙烧10~14小时,即得。
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Application publication date: 20210112 |