CN116328821A - 一种介孔化原位晶化fcc催化剂及其制备方法 - Google Patents
一种介孔化原位晶化fcc催化剂及其制备方法 Download PDFInfo
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
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- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 2
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- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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Abstract
本发明提供了一种介孔化原位晶化FCC催化剂及其制备方法,包括如下步骤:(1)将金属盐、螯合剂和去离子水充分混合后于40℃~80℃温度下持续搅拌反应0.5~2小时,加入高岭土继续搅拌反应1~4小时,冷却至室温后用稀盐酸调节体系pH=3~6,加入铝溶胶混合均匀,然后喷雾干燥成型,得高岭土微球;(2)将(1)所得粘土微球于600℃~900℃温度下焙烧1~4小时,得活化高岭土微球;(3)将(2)所得活化高岭土微球、水玻璃、NaY分子筛合成导向剂、氢氧化钠和去离子水混合均匀,然后转移至高压釜中于80℃~150℃温度下静置晶化6~48小时,冷却至室温后,过滤、洗涤和干燥后即得介孔化原位晶化FCC催化剂。
Description
技术领域
本发明涉及一种原位晶化FCC催化剂及其制备方法,具体涉及一种含有丰富介孔孔道结构的原位晶化FCC催化剂及其制备方法。
背景技术
流化催化裂化(FCC)是中国原油二次加工的主要手段,生产了中国70%的汽油,FCC催化剂是催化裂化的核心技术。FCC催化剂主要分两种类型,半合成催化剂和原位晶化型催化剂。原位晶化型催化剂最早报道于20世纪70年代,其通过首先制备高岭土微球,随后在微球上原位晶化生长Y型分子筛得到。相对于半合成型FCC催化剂,原位晶化FCC催化剂具有重油转化能力强、抗重金属污染性能好的特点。然而,随着世界范围内原油日益重质化和劣质化,对FCC催化剂的性能提出了越来越高的要求。由于目前原位晶化FCC催化剂大多以高岭土为基质材料,而高岭土材料通常缺乏必要的孔结构,尤其是适合重油分子传质扩散的介孔孔道,这也使得当前原位晶化FCC催化剂已难以满足原油性质变化对FCC催化剂的性能需求。
发明内容
针对上述问题,本发明的目的在于提供一种含有丰富介孔孔道结构的介孔化原位晶化FCC催化剂及其制备方法。
本发明公开的一种介孔化原位晶化FCC催化剂制备方法,所述制备方法包括如下步骤:
(1)将金属盐、螯合剂和去离子水充分混合后于40℃~80℃温度下持续搅拌反应0.5~2小时,加入高岭土继续搅拌反应1~4小时,冷却至室温后用稀盐酸调节体系pH=3~6,加入铝溶胶混合均匀,然后喷雾干燥成型,得高岭土微球;
(2)将(1)所得粘土微球于600℃~900℃温度下焙烧1~4小时,得活化高岭土微球;
(3)将(2)所得活化高岭土微球、水玻璃、NaY分子筛合成导向剂、氢氧化钠和去离子水混合均匀,然后转移至高压釜中于80℃~150℃温度下静置晶化6~48小时,冷却至室温后,过滤、洗涤和干燥后即得所述的一种介孔化原位晶化FCC催化剂。
本发明提供的制备方法中,步骤(1)中所述金属盐可选自氯化铝、硝酸铝、硫酸铝、氯化钇、硝酸钇、氯化镧、硝酸镧、氯化铈、硝酸铈中的一种或几种,优选硝酸镧。
本发明提供的制备方法中,步骤(1)中所述螯合剂可选自甲醇胺、乙醇胺、丙醇胺、二乙醇胺和三乙醇胺中的一种或几种,优选乙醇胺。
本发明提供的制备方法中,步骤(1)中所述高岭土:铝溶胶(按Al2O3计):金属盐(按金属氧化物计):螯合剂:去离子水质量比=1:0.01~0.15:0.001~0.15:0.001~0.05:2~20,优选1:0.05~0.10:0.01~0.10:0.01~0.03:4~8。
本发明提供的制备方法中,步骤(3)中所述活化高岭土微球:水玻璃(按所含固体质量计):NaY分子筛合成导向剂(按所含固体质量计):氢氧化钠:去离子水=1:0.005~0.2:0.001~0.30:0.005~0.20:0.5~5,优选1:0.05~0.1:0.05~0.15:0.05~0.10:1~3。
本发明提供的制备方法中,步骤(1)中所述喷雾干燥成型为本领域通用技术工艺。
本发明一种介孔化原位晶化FCC催化剂,按照如上述制备方法制作所得。
本发明以大尺寸的有机配体螯合金属阳离子离子为交换阳离子,通过阳离子交换使其进入到高岭土的层间结构当中,对高岭土进行层间柱撑改性,从而能够显著增加高岭土的内部孔道结构,尤其是介孔尺度孔道结构,极大地改善了高岭土作为原位晶化FCC催化剂基质材料的孔结构性质,能够显著增加所制备原位晶化FCC催化剂所含的介孔孔道结构,提高其催化裂化反应性能,具备良好的应用前景。
具体实施方式
下面结合实施例对本发明作进一步的说明,但本发明并不局限于下述实施例。
原料来源及主要指标:
高岭土、铝溶胶(Al2O3含量:18重%)、水玻璃(固含量:19.8重%)、NaY分子筛合成导向剂(固含量:25重%)和原位晶化FCC催化剂(LB-5)购自国内某催化剂生产企业,合格工业品。乙醇胺(NH2CH2CH2OH)、氢氧化钠(NaOH)和硝酸镧(La(NO3)3·6H2O),均为市售分析纯试剂。
分析和评价:
催化剂样品的比表面和孔体积参数测定在美国Micromeritics公司生产的ASAP3000型N2吸附-脱附仪上进行。催化剂样品经铵离子和稀土离子交换后在ACE(Advanced cracking evaluation,Kayser R+MultiMode微型反应器)装置上评价其重油催化裂化反应性能。反应温度530℃,剂油比5,800℃、100%水蒸气老化,原料油性质如表1所示。
表1原料油性质
实施例1
本实施例提供的一种介孔化原位晶化FCC催化剂的制备方法,步骤如下:
(1)将10.6克六水硝酸镧、2克乙醇胺和800克去离子水充分混合后于40℃温度下持续搅拌反应2小时,加入200克高岭土继续搅拌反应4小时,冷却至室温后用稀盐酸调节体系pH=3.5,加入55.6克铝溶胶混合均匀,然后喷雾干燥成型,得高岭土微球。
(2)将(1)所得粘土微球于650℃温度下焙烧4小时,得活化高岭土微球。
(3)将100克(2)所得活化高岭土微球、25.3克水玻璃、20克NaY分子筛合成导向剂、5克氢氧化钠和100克去离子水混合均匀,然后转移至高压釜中于80℃温度下静置晶化48小时。冷却至室温后,过滤、洗涤和干燥后即得所述的一种介孔化原位晶化FCC催化剂C1。
实施例2
本实施例提供的一种介孔化原位晶化FCC催化剂的制备方法,步骤如下:
(1)将47.9克六水硝酸镧、6克乙醇胺和1800克去离子水充分混合后于60℃温度下持续搅拌反应1小时,加入300克高岭土继续搅拌反应2小时,冷却至室温后用稀盐酸调节体系pH=4.5,加入116.7克铝溶胶混合均匀,然后喷雾干燥成型,得高岭土微球。
(2)将(1)所得粘土微球于750℃温度下焙烧2小时,得活化高岭土微球。
(3)将200克(2)所得活化高岭土微球、70.7克水玻璃、80克NaY分子筛合成导向剂、14克氢氧化钠和400克去离子水混合均匀,然后转移至高压釜中于120℃温度下静置晶化24小时。冷却至室温后,过滤、洗涤和干燥后即得所述的一种介孔化原位晶化FCC催化剂C2。
实施例3
本实施例提供的一种介孔化原位晶化FCC催化剂的制备方法,步骤如下:
(1)将106.3克六水硝酸镧、12克乙醇胺和3200克去离子水充分混合后于80℃温度下持续搅拌反应0.5小时,加入400克高岭土继续搅拌反应1小时,冷却至室温后用稀盐酸调节体系pH=5.5,加入222.2克铝溶胶混合均匀,然后喷雾干燥成型,得高岭土微球。
(2)将(1)所得粘土微球于850℃温度下焙烧1小时,得活化高岭土微球。
(3)将300克(2)所得活化高岭土微球、151.5克水玻璃、180克NaY分子筛合成导向剂、30克氢氧化钠和900克去离子水混合均匀,然后转移至高压釜中于150℃温度下静置晶化6小时。冷却至室温后,过滤、洗涤和干燥后即得所述的一种介孔化原位晶化FCC催化剂C3。
根据上述三个实施例,表2列出了不同原位晶化FCC催化剂样品的孔结构参数。可以看出,与传统原位晶化工艺制备的LB-5催化剂相比,本发明方法制备的介孔化原位晶化FCC催化剂样品均显示出了显著更高的介孔体积和总孔体积,具备优良的介孔孔结构性质。
表2催化剂样品孔结构参数
表3列出了不同原位晶化FCC催化剂样品的重油催化裂化反应性能。可以看出,与传统原位晶化工艺制备的LB-5催化剂相比,本发明方法制备的介孔化原位晶化FCC催化剂显示出了明显更为优异的催化裂化反应性能,具备显著更强的重油转化能力以及更高的轻质油品收率。
表3催化剂样品的重油催化裂化反应性能
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (6)
1.一种介孔化原位晶化FCC催化剂制备方法,包括如下步骤:
(1)将金属盐、螯合剂和去离子水充分混合后于40℃~80℃温度下持续搅拌反应0.5~2小时,加入高岭土继续搅拌反应1~4小时,冷却至室温后用稀盐酸调节体系pH=3~6,加入铝溶胶混合均匀,然后喷雾干燥成型,得高岭土微球,高岭土:铝溶胶(按Al2O3计):金属盐(按金属氧化物计):螯合剂:去离子水的质量比=1:0.01~0.15:0.001~0.15:0.001~0.05:2~20;
(2)将(1)所得粘土微球于600℃~900℃温度下焙烧1~4小时,得活化高岭土微球;
(3)将(2)所得活化高岭土微球、水玻璃、NaY分子筛合成导向剂、氢氧化钠和去离子水混合均匀,活化高岭土微球:水玻璃(按所含固体质量计):NaY分子筛合成导向剂(按所含固体质量计):氢氧化钠:去离子水=1:0.005~0.2:0.001~0.30:0.005~0.20:0.5~5,然后转移至高压釜中于80℃~150℃温度下静置晶化6~48小时,冷却至室温后,过滤、洗涤和干燥后即得所述介孔化原位晶化FCC催化剂。
2.根据权利要求1所述制备方法,其特征在于:所述步骤(1)中的金属盐可选自氯化铝、硝酸铝、硫酸铝、氯化钇、硝酸钇、氯化镧、硝酸镧、氯化铈、硝酸铈中的一种或几种。
3.根据权利要求1所述制备方法,其特征在于:所述步骤(1)中的螯合剂可选自甲醇胺、乙醇胺、丙醇胺、二乙醇胺和三乙醇胺中的一种或几种。
4.根据权利要求1所述制备方法,其特征在于:所述步骤(1)中的高岭土:铝溶胶(按Al2O3计):金属盐(按金属氧化物计):螯合剂:去离子水的质量比=1:0.05~0.10:0.01~0.10:0.01~0.03:4~8。
5.根据权利要求1所述制备方法,其特征在于:所述步骤(3)中的活化高岭土微球:水玻璃(按所含固体质量计):NaY分子筛合成导向剂(按所含固体质量计):氢氧化钠:去离子水=1:0.05~0.1:0.05~0.15:0.05~0.10:1~3。
6.一种介孔化原位晶化FCC催化剂,其特征在于:按照如权利要求1-5任意一项所述的制备方法制作所得。
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