CN111573689A - 一种usy分子筛及其制备方法 - Google Patents
一种usy分子筛及其制备方法 Download PDFInfo
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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 title claims abstract description 122
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000012065 filter cake Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000004537 pulping Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 150000007524 organic acids Chemical class 0.000 claims abstract description 13
- 238000005342 ion exchange Methods 0.000 claims abstract description 11
- 238000010306 acid treatment Methods 0.000 claims abstract description 9
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- -1 cationic quaternary ammonium salt Chemical class 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 22
- 235000019270 ammonium chloride Nutrition 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 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
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 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
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- XCOHAFVJQZPUKF-UHFFFAOYSA-M octyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](C)(C)C XCOHAFVJQZPUKF-UHFFFAOYSA-M 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- AQZSPJRLCJSOED-UHFFFAOYSA-M trimethyl(octyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)C AQZSPJRLCJSOED-UHFFFAOYSA-M 0.000 claims description 2
- FCGQIZKUTMUWDC-UHFFFAOYSA-M trimethyl(propyl)azanium;bromide Chemical compound [Br-].CCC[N+](C)(C)C FCGQIZKUTMUWDC-UHFFFAOYSA-M 0.000 claims description 2
- NRWCNEBHECBWRJ-UHFFFAOYSA-M trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)C NRWCNEBHECBWRJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 24
- 238000004523 catalytic cracking Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 239000000295 fuel oil Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 7
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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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
- 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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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
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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
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
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Abstract
一种USY分子筛及其制备方法,所述制备方法包括以下步骤:(1)将NaY分子筛原料与铵盐溶液混合进行铵离子交换,然后经过滤、洗涤后得到NH4Y分子筛滤饼;(2)将步骤(1)得到的NH4Y分子筛滤饼、阳离子季铵盐和去离子水混合、打浆,于60~90℃温度下持续搅拌0.5~3小时,然后过滤、洗涤。各物料用量按季铵盐:NaY分子筛(干基):去离子水质量比=0.01~0.1:1:5~30计;(3)对步骤(2)得到的分子筛用有机酸溶液进行酸处理;(4)对步骤(3)所得分子筛进行高温水汽处理,即得所述USY分子筛。
Description
技术领域
本发明涉及一种USY分子筛及其制备方法,更具体地说涉及一种用于催化裂化反应低晶胞、高结晶度USY分子筛及其制备方法。
背景技术
催化裂化(FCC)是炼油工业最重要的重油轻质化手段,也是催化剂用量最大的原油二次加工过程。随着原油重质化、劣质化以及市场对轻质油品需求量的增加,炼油厂为提高重质原料油催化裂化深度加工的能力,对催化裂化催化剂的质量提出了更高的要求。Y型分子筛具有适宜的酸性、极高的比表面积和良好的热稳定性,是工业FCC催化剂的主要活性组分,分子筛的裂化活性和选择性直接影响催化裂化装置的产品分布和经济效益。
由于催化裂化高温水热的反应条件,从而要求催化裂化催化剂尤其是其活性组分Y型分子筛具有良好的水热稳定性。为了提高Y型分子筛的水热稳定性,上世纪60年代人们开始对Y型分子筛进行超稳化处理,即在高温焙烧条件下通入100%水蒸气对Y型分子筛进行处理,以脱除Y型分子筛部分骨架铝,提高Y型分子筛骨架硅铝比,进而达到收缩Y型分子筛晶胞、提高分子筛水热稳定性的目的,由此制备的超稳Y型分子筛即为USY分子筛。通常,为了获得低晶胞、高结晶度的USY分子筛,在超稳化处理前,一般需要采用有机酸(多为草酸和柠檬酸)对Y型分子筛进行酸处理,以脱除分子筛结构当中的非骨架铝物种,这样将有利于后续超稳定化处理,从而获得低晶胞、高结晶度的USY分子筛。
然而,在上述酸处理过程中,有机酸在脱除分子筛表面非骨架铝物种的同时,不可避免地会脱除部分骨架铝物种,这会破坏分子筛结构,造成分子筛结晶度下降,不利于获得低晶胞、高结晶度的USY分子筛。因此,如何改进现有USY分子筛制备工艺,在缩小分子筛晶胞的同时尽可能地提高分子筛结晶度一直是一项具有挑战性的工作,这对催化裂化催化剂技术领域具有重要意义。
发明内容
针对上述存在的问题,本发明的目的是提供一种简单易行的制备低晶胞、高结晶度USY分子筛及其制备方法,并且将USY分子筛制备成催化裂化催化剂。相对于传统方法制备的USY分子筛,所提供的USY分子筛不但具有良好的水热稳定性,同时还具有更低的晶胞以及更高的结晶度,所制备催化裂化催化剂显示了更高的重油转化能力。
本发明提供了一种USY分子筛及其制备方法,制备方法包括以下步骤:
(1)将NaY分子筛原料与铵盐溶液混合进行铵离子交换,然后经过滤、洗涤后得到NH4Y分子筛滤饼;
(2)将步骤(1)得到的NH4Y分子筛滤饼、阳离子季铵盐和去离子水混合、打浆,于60~90℃温度下持续搅拌0.5~3小时,然后过滤、洗涤。各物料用量按季铵盐:NaY分子筛(干基):去离子水质量比=0.01~0.1:1:5~30计;
(3)对步骤(2)得到的分子筛用有机酸溶液进行酸处理;
(4)对步骤(3)所得分子筛进行高温水汽处理,即得所述USY分子筛。
本发明提供的制备方法中,步骤(1)中所述的铵离子交换为:按照铵盐:NaY分子筛(干基):去离子水=0.1~0.3:1:5~30的质量比将铵盐、NaY分子筛和去离子水混合、打浆,调节浆液pH≈3.5,于60~90℃温度下交换1~3小时。
本发明提供的制备方法中,步骤(1)中所述铵盐可选自氯化铵、硫酸铵、硝酸铵、硫酸氢铵、磷酸铵、磷酸一氢铵、磷酸二氢铵、草酸铵、柠檬酸铵和乙酸铵中的一种或几种,优选氯化铵。
本发明提供的制备方法中,步骤(2)中所述阳离子季铵盐可选自四甲溴化铵、四甲基氯化铵、丙基三甲基溴化铵、丙基三甲基氯化铵、四乙基溴化铵、四乙基氯化铵、四丙基溴化铵、四丙基氯化铵、辛基三甲基溴化铵、辛基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基氯化铵、十六烷基三甲基溴化铵和十六烷基三甲基氯化铵中的一种或几种,优选十六烷基三甲基溴化铵。
本发明提供的制备方法中,步骤(3)中所述酸处理过程为:按有机酸:NaY分子筛(干基):去离子水质量比=0.005~0.05:1:5~30计,将有机酸、去离子水和步骤(2)所得分子筛混合、打浆,然后于40~80℃温度下持续搅拌反应1~3小时,然后过滤、洗涤、干燥。
本发明提供的制备方法中,步骤(3)中所述有机酸可选自甲酸、乙酸、草酸、柠檬酸、酒石酸、枸椽酸、抗坏血酸中的一种或几种,优选柠檬酸。
本发明提供的制备方法中,步骤(4)中所述高温水汽处理为在100%水蒸气条件下对物料进行高温焙烧,焙烧温度为500~700℃,焙烧时间为1~4小时。
不同于现有USY分子筛制备方法,本发明方法在对Y型分子筛进行酸处理脱除非骨架硅物种操作前,以阳离子季铵盐溶液对分子筛进行处理,处理过程中季铵阳离子大分子与分子筛骨架铝物种通过正负电荷作用结合,由于季铵阳离子大分子巨大的空间位阻效应,可以显著减少后续有机酸处理过程中有机酸对分子筛的骨架铝物种的破坏,从而能够有效保护分子筛骨架结构,提高分子筛的结晶度。
具体实施方式
下面结合实施例对本发明作进一步的说明,但本发明保护范围并不受这些实例的限制。
(1)原料及规格
NaY分子筛、铝溶胶(Al2O3含量19.40重%)、高岭土,合格工业品;
氯化铵、柠檬酸、十六烷基三甲基溴化铵、分析纯,国药集团。
(2)晶胞和结晶度分析
分子筛的结晶度、晶胞参数在日本Rigaku公司生产的D/max-2200PC型x射线衍射仪上分析。
(3)催化剂重油催化裂化反应性能评价
催化剂预先在800℃、100%水蒸气条件下处理17小时。在ACE(Advanced crackingevaluation,产地:美国)装置上评价催化剂样品的重油催化裂化反应性能。装置反应温度为510℃,催化剂/原料油质量比为5。
对比例1
传统方法制备USY分子筛。
(1)将100克NaY分子筛(干基)、10克氯化铵和800克去离子水混合、打浆,调节浆液pH≈3.5,于90℃温度下离子交换1小时,然后过滤、洗涤,得NH4Y滤饼。
(2)将步骤(2)所得NH4Y分子筛滤饼、10克柠檬酸、3000克去离子水混合、打浆,于50℃温度下持续搅拌处理3小时,然后过滤、洗涤、干燥。
(3)将步骤(2)所得分子筛于100%水蒸气、550℃条件下焙烧4小时,即得产品。
对比例2
传统方法制备USY分子筛。
(1)将100克NaY分子筛(干基)、20克氯化铵和1500克去离子水混合、打浆,调节浆液pH≈3.5,于80℃温度下离子交换1.5小时,然后过滤、洗涤,得NH4Y分子筛滤饼。
(2)将步骤(1)所得NH4Y分子筛滤饼、7克柠檬酸、2000克去离子水混合、打浆,于80℃温度下持续搅拌处理1小时,然后过滤、洗涤、干燥。
(3)将步骤(2)所得分子筛于100%水蒸气、650℃条件下焙烧2小时,即得产品。
对比例3
传统方法制备USY分子筛。
(1)将100克NaY分子筛(干基)、30克氯化铵和3000克去离子水混合、打浆,调节浆液pH≈3.5,于65℃温度下离子交换3小时,然后过滤、洗涤,得NH4Y分子筛滤饼。
(2)将步骤(1)所得NH4Y分子筛滤饼、3克柠檬酸、1000克去离子水混合、打浆,于70℃温度下持续搅拌处理1.5小时,然后过滤、洗涤、干燥。
(3)将步骤(2)所得NH4Y分子筛于100%水蒸气、700℃条件下焙烧1小时,即得产品。
实施例1
本发明方法制备USY分子筛。
(1)将100克NaY分子筛(干基)、10克氯化铵和800克去离子水混合、打浆,调节浆液pH≈3.5,于90℃温度下离子交换1小时,然后过滤、洗涤,得NH4Y分子筛滤饼。
(2)将步骤(1)所得NH4Y分子筛滤饼、6克十六烷基三甲基溴化铵和1500克去离子水混合、打浆,于75℃温度下持续搅拌反应2小时,然后过滤、洗涤,得分子筛滤饼。
(3)将步骤(2)所得分子筛滤饼、10克柠檬酸、3000克去离子水混合、打浆,于50℃温度下持续搅拌处理3小时,然后过滤、洗涤、干燥。
(4)将步骤(3)所得分子筛于100%水蒸气、550℃条件下焙烧4小时,即得产品。
实施例2
本发明方法制备USY分子筛。
(1)将100克NaY分子筛(干基)、20克氯化铵和1500克去离子水混合、打浆,调节浆液pH≈3.5,于80℃温度下离子交换1.5小时,然后过滤、洗涤,得NH4Y分子筛滤饼。
(2)将步骤(1)所得NH4Y分子筛滤饼、3克十六烷基三甲基溴化铵和800克去离子水混合、打浆,于90℃温度下持续搅拌反应0.5小时,然后过滤、洗涤,得分子筛滤饼。
(3)将步骤(2)所得分子筛滤饼、7克柠檬酸、2000克去离子水混合、打浆,于80℃温度下持续搅拌处理1小时,然后过滤、洗涤、干燥。
(4)将步骤(3)所得分子筛于100%水蒸气、650℃条件下焙烧2小时,即得产品。
实施例3
本发明方法制备USY分子筛。
(1)将100克NaY分子筛(干基)、30克氯化铵和3000克去离子水混合、打浆,调节浆液pH≈3.5,于65℃温度下离子交换3小时,然后过滤、洗涤,得NH4Y分子筛滤饼。
(2)将步骤(1)所得NH4Y分子筛滤饼、9克十六烷基三甲基溴化铵和2800克去离子水混合、打浆,于65℃温度下持续搅拌反应3小时,然后过滤、洗涤,得分子筛滤饼。
(3)将步骤(2)所得分子筛滤饼、25克高岭土(干基)、3克柠檬酸、1000克去离子水混合、打浆,于70℃温度下持续搅拌处理1.5小时,然后过滤、洗涤、干燥。
(4)将步骤(3)所得分子筛于100%水蒸气、700℃条件下焙烧1小时,即得产品。
实施例4
以对比例制备的USY分子筛为活性组分制备催化裂化催化剂。
按USY分子筛、铝溶胶和高岭土干基含量分别为35重%、13重%和52重%计,将350克对比例2制备的USY分子筛(干基)、670克铝溶胶、520克高岭土(干基)和2100克去离子水混合、打浆,然后喷雾干燥成型,焙烧固化后即得催化裂化催化剂。
实施例5
以本发明方法制备的USY分子筛为活性组分制备催化裂化催化剂。
按USY分子筛、铝溶胶和高岭土干基含量分别为35重%、13重%和52重%计,将402克实施例2制备的混合固料(干基,含350克USY分子筛和52克高岭土)、670克铝溶胶、468克高岭土(干基)和2100克去离子水混合、打浆,然后喷雾干燥成型,焙烧固化后即得催化裂化催化剂。
表1不同USY分子筛样品晶胞参数和结晶度数据。
表1给出了不同USY分子筛样品晶胞参数和结晶度数据,可以看出,与常规方法制备的USY分子筛相比(对比例1~对比例3),本发明方法制备的USY分子筛样品(实施例1~实施例3)具有显著更低的晶胞参数以及更高的结晶度。上述结果表明,本发明方法可以有效减少现有常规方法制备USY过程中对分子筛结构的破坏,可以获得低晶胞、高结晶度的USY分子筛。
表2催化剂重油催化裂化反应性能。
催化剂 | 实施例4 | 实施例5 |
干气,% | 2.04 | 2.24 |
液化气,% | 19.73 | 21.08 |
汽油,% | 51.52 | 52.79 |
柴油,% | 12.97 | 11.68 |
重油,% | 6.26 | 5.09 |
焦炭,% | 6.48 | 7.12 |
转化率,% | 80.77 | 83.23 |
表2列出了所制备催化裂化催化剂样品的重油催化裂化反应性能,可以看出,在分子筛含量相同的条件下,使用本发明方法制备分子筛催化剂(实施例5)的重油催化裂化反应性能要明显优于使用传统方法制备分子筛催化剂(实施例4)。与实施例4催化剂相比,实施例5催化剂的重油收率降低了1.17个百分点,转化率提高了2.46个百分点,具有显著更强的重油转化能力。
Claims (7)
1.一种USY分子筛及其制备方法,其特征在于所述制备方法包括以下步骤:
(1)将NaY分子筛原料与铵盐溶液混合进行铵离子交换,然后经过滤、洗涤后得到NH4Y分子筛滤饼;
(2)将步骤(1)得到的NH4Y分子筛滤饼、阳离子季铵盐和去离子水混合、打浆,于60~90℃温度下持续搅拌0.5~3小时,然后过滤、洗涤。各物料用量按季铵盐:NaY分子筛(干基):去离子水质量比=0.01~0.1:1:5~30计;
(3)对步骤(2)得到的分子筛用有机酸溶液进行酸处理;
(4)对步骤(3)所得分子筛进行高温水汽处理,即得所述USY分子筛。
2.根据权利要求1所述制备方法,其特征在于步骤(1)中所述的铵离子交换过程为:按照铵盐:NaY分子筛(干基):去离子水=0.1~0.3:1:5~30的质量比将铵盐、NaY分子筛和去离子水混合、打浆,调节浆液pH≈3.5,于60~90℃温度下交换1~3小时。
3.根据权利要求1所述制备方法,其特征在于步骤(1)中所述铵盐可选自氯化铵、硫酸铵、硝酸铵、硫酸氢铵、磷酸铵、磷酸一氢铵、磷酸二氢铵、草酸铵、柠檬酸铵和乙酸铵中的一种或几种,优选氯化铵。
4.根据权利要求1所述制备方法,其特征在于步骤(2)中所述阳离子季铵盐可选自四甲溴化铵、四甲基氯化铵、丙基三甲基溴化铵、丙基三甲基氯化铵、四乙基溴化铵、四乙基氯化铵、四丙基溴化铵、四丙基氯化铵、辛基三甲基溴化铵、辛基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基氯化铵、十六烷基三甲基溴化铵和十六烷基三甲基氯化铵中的一种或几种,优选十六烷基三甲基溴化铵。
5.根据权利要求1所述制备方法,其特征在于步骤(3)中所述酸处理过程为:按有机酸:NaY分子筛(干基):去离子水质量比=0.005~0.05:1:5~30计,将有机酸、去离子水和步骤(2)所得分子筛混合、打浆,然后于40~80℃温度下持续搅拌反应1~3小时,然后过滤、洗涤、干燥。
6.根据权利要求1所述制备方法,其特征在于步骤(3)中所述有机酸可选自甲酸、乙酸、草酸、柠檬酸、酒石酸、枸椽酸、抗坏血酸中的一种或几种,优选柠檬酸。
7.根据权利要求1所述制备方法,其特征在于步骤(4)中所述高温水汽处理为在100%水蒸气条件下对物料进行高温焙烧,焙烧温度为500~700℃,焙烧时间为1~4小时。
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