CN104245136A - 具有增强的活性和水热稳定性的磷改性裂化催化剂 - Google Patents
具有增强的活性和水热稳定性的磷改性裂化催化剂 Download PDFInfo
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- CN104245136A CN104245136A CN201280066003.4A CN201280066003A CN104245136A CN 104245136 A CN104245136 A CN 104245136A CN 201280066003 A CN201280066003 A CN 201280066003A CN 104245136 A CN104245136 A CN 104245136A
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- zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 45
- 239000011574 phosphorus Substances 0.000 title claims abstract description 42
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 230000000694 effects Effects 0.000 title description 10
- 238000005336 cracking Methods 0.000 title description 3
- 239000011734 sodium Substances 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 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 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 60
- 239000010457 zeolite Substances 0.000 claims description 54
- 229910021536 Zeolite Inorganic materials 0.000 claims description 53
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 50
- 239000005995 Aluminium silicate Substances 0.000 claims description 38
- 235000012211 aluminium silicate Nutrition 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 32
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 25
- -1 rare-earth cation Chemical class 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000002910 rare earth metals Chemical class 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 8
- 150000003863 ammonium salts Chemical group 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000004927 clay Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000005696 Diammonium phosphate Substances 0.000 description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 10
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 10
- 235000019838 diammonium phosphate Nutrition 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000004231 fluid catalytic cracking Methods 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000012013 faujasite Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019795 sodium metasilicate Nutrition 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 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 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 1
- 229960005286 carbaryl Drugs 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- 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
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/106—Y-type faujasite
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C—CHEMISTRY; METALLURGY
- 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
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- C01B39/24—Type Y
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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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- 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
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B01J29/00—Catalysts comprising molecular sieves
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- Life Sciences & Earth Sciences (AREA)
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Abstract
本发明提供FCC催化剂的磷修饰,所述磷修饰通过如下方式进行:减少形成后未处理的(as-formed)催化剂的钠含量、用磷酸盐溶液进行第一次处理,进行第二次铵交换从而进一步减少磷溶液处理的催化剂的钠含量,并用磷酸盐溶液进行第二次处理。
Description
发明领域
本发明涉及由高岭土原料制成的含磷催化剂并且涉及利用所述催化剂的烃催化裂化工艺。
发明背景
催化裂化是商业上以很大规模应用的石油精炼工艺。在美国,约50%的炼油厂汽油共混池是通过这种工艺生产,几乎所有都是利用流化催化裂化(FCC)工艺生产。目前,所有市售FCC催化剂都在二氧化硅、氧化铝、二氧化硅-氧化铝、高岭土、粘土等的非晶或非晶/高岭土基质中含有结晶铝硅酸盐沸石,特别是合成的八面沸石,即,Y型沸石。
已经做了许多工作来增加沸石的热-蒸汽(水热)稳定性,通过引入稀土离子或铵离子经由离子交换技术来降低对Y型沸石有破坏性的苏打含量。热和化学改性的Y型沸石,诸如超稳Y型沸石Y(USY)和煅烧稀土交换Y型沸石(CREY)在商业上用于将重质烃原料转化成更有价值的产品。
在流化催化裂化催化剂的现有技术中,活性沸石组分是通过两种通用技术之一掺入到催化剂微球中。在一种技术中,使沸石组分结晶,然后在单独的步骤中将其掺入到微球中。在第二种技术,即原位技术中,首先形成微球,然后使沸石组分在微球自身中结晶从而得到含有沸石和非沸石组分的微球。
长期以来已经认识到:对于要在商业上获得成功的流体催化裂化催化剂,它必须具有商业上可接受的活性、选择性和稳定性的特征。它必须具有足够活性以经济地产生有吸引力的产率、必须具有对于生成期望的产物以及不生成不期望的产物的良好的选择性、并且必须足够水热稳定和耐磨从而具有商业上有效的寿命。
美国专利第4,493,902号(其教导的内容通过交叉引用并入在此)公开了新的流体催化裂化催化剂,所述催化剂包含耐磨的高沸石含量催化活性微球,所述微球含有大于约40重量%,优选50-70重量%的Y型八面沸石;还公开了通过在多孔微球中使大于约40%的钠Y沸石结晶而制备此类催化剂的方法,所述多孔微球由两种不同形式的具有化学反应性的煅烧粘土的混合物组成,所述两种不同形式的具有化学反应性的煅烧粘土为偏高岭土(经煅烧而经历伴随脱羟基作用的强放热反应的高岭土)和在比用于将高岭土转化为偏高岭土的条件更为苛刻的条件下煅烧的高岭粘土,即经煅烧而经历特征高岭土放热反应的高岭粘土,有时也称为尖晶石型煅烧高岭土。在优选实施方案中,将含有两种形式煅烧高岭粘土的微球浸没在碱性硅酸钠溶液中,将其加热,优选加热至可获得的最大量Y八面沸石在微球中结晶。
在′902技术的实施中,沸石在其中结晶的多孔微球优选通过形成与较少量硅酸钠在一起的粉末状原生(水合)高岭粘土(Al2O3∶2SiO2∶2H2O)和已经历放热反应的粉末状煅烧高岭粘土的含水浆料来制备,其中硅酸钠作为装入喷雾干燥器中以形成微球的浆料的流化剂,并然后起到使喷雾干燥的微球的组分具有物理完整性的作用。然后,将含有水合高岭粘土与经煅烧而经历放热反应的高岭土的混合物的喷雾干燥微球在不如使高岭土经历放热反应所需要的条件那样苛刻的受控条件下煅烧,以便使微球的水合高岭粘土部分脱水并使其转化为偏高岭土,这样得到含有期望的偏高岭土、经煅烧而经历放热反应的高岭土及硅酸钠粘合剂的混合物的微球。在′902专利的说明实施例中,在喷雾干燥器的进料中存在大约等重量的水合高岭土和尖晶石,并且所得煅烧微球包含的经历放热反应的高岭土稍多于偏高岭土。′902专利教导指出煅烧微球包含约30-60重量%的偏高岭土和约40-70重量%的以其特征性放热反应为特征的高岭土。所述专利中描述的次优选方法涉及对含有预先煅烧至偏高岭土状态的高岭粘土与经煅烧而经历放热反应的高岭土的混合物的浆料进行喷雾干燥,但所述浆料中不包括任何水合高岭土,因而直接提供既含有偏高岭土又含有经煅烧而经历放热反应的高岭土的微球,而不必通过煅烧将水合高岭土转化为偏高岭土。
在实施′902专利中描述的发明时,在结晶引发剂(晶种)的存在下,使由经缎烧而经历放热反应的高岭土和偏高岭土组成的微球与腐蚀性的富集硅酸钠溶液反应,从而将微球中的二氧化硅和氧化铝转化为合成的钠八面沸石(Y型沸石)。从硅酸钠母液中分离出微球,将其与稀土、铵离子或者这两者进行离子交换,从而形成稀土形式或多种已知稳定形式的催化剂。′902专利的技术提供了获得理想而独特的具有高沸石含量和高活性、良好的选择性和热稳定性以及耐磨性的组合的方式。
前面提到的技术已取得了广泛的商业成功。由于可以获得具有耐磨性的高沸石含量的微球,因此要求特殊性能(诸如提高活性和/或选择性而不引起昂贵的机械再设计)的炼油厂现可以获得定制设计的催化剂。目前提供给国内外炼油厂的相当一大部分FCC催化剂都基于这种技术。
包括磷或磷化合物的催化剂已描述在美国专利第4,498,975号、第4,504,382号、第4,839,319号、第5,110,776号中。这些参考文献公开了沸石催化剂的催化裂化活性和选择性可通过添加磷来改进。
例如,根据U.S.4,454,241中公开的发明,提供了包含由粘土原料制成的结晶铝硅酸盐沸石、来源于所述粘土的残渣及有效量的磷的催化剂,所述催化剂已通过包括以下的步骤制备:(a)使粘土来源的含碱金属的Y型结晶铝硅酸盐沸石和粘土来源的残渣与非碱金属阳离子进行离子交换从而减少所述含碱金属沸石的碱金属含量;(b)煅烧所得经离子交换的沸石和粘土来源的残渣;及(c)使所得煅烧的沸石和粘土来源的残渣与包含选自由磷酸二氢阴离子、亚磷酸二氢阴离子及其混合物组成的组的阴离子的介质接触,持续足以使有效量的磷与所述煅烧的沸石和残渣复合的时间。
U.S.5,378,670公开了磷改性沸石/分子筛的制备,其中使氢、铵部分交换的钠沸石/分子筛与诸如H3PO4的磷化合物组合从而获得含磷沸石/分子筛组合物,对所述组合物进行热处理(蒸制)从而获得磷发生反应的沸石/分子筛,随后使所述磷发生反应的沸石/分子筛与另外的磷化合物反应从而获得含有约2重量%至7重量%的P2O5的磷处理的沸石/分子筛。提供蒸制是为了产生单胞尺寸相对于原料较小的超稳沸石。
发明概述
根据本发明,流化裂化催化剂的磷改性使得催化剂具有高水热稳定性和活性。
本发明的催化剂微球是通过如共同转让的美国专利第4,493,902号中公开的一般工艺生产。在结晶过程终止后,通过过滤将含有Y型八面沸石的微球从母液中分离出来。通常,所述微球含有大于约8重量%的Na2O。通过氨离子交换将Na2O减少至约2重量%。将所述部分交换的材料加入到180°F的pH为2-5的磷酸盐溶液中从而在催化剂上产生约0.5%至2%P2O5。在过滤和洗涤后,然后在180°F下对样品进行稀土交换从而在催化剂上产生0.25-1.5%REO。
将稀土交换的材料干燥并煅烧,并进行进一步的氨离子交换从而将Na2O减少至约0.2%。再次将所得材料加入到180°F的pH为2-5的磷酸盐溶液中从而在催化剂上产生约2-4%P2O5。
发明详述
本发明的催化剂包含如例如在前面提到的U.S.4,493,902中描述的从高岭土原料原位获得的Y型结晶铝硅酸盐沸石。所述催化剂包含有效量的磷,用以相对于相同但未通过指定的方法掺入磷的催化剂增强所述催化剂的活性。按P2O5计算,以沸石加高岭土来源的基质的重量为基准,所述催化剂中存在的磷的合适的量包括至少约2.0重量%,优选至少约2.8重量%,更优选约2.8重量%至约3.5重量%的磷。“Y型沸石”在本文意指具有八面沸石的结构并且具有至少约3∶1的二氧化硅与氧化铝摩尔比的结晶铝硅酸盐沸石。
本发明催化剂的特征在于它的用于掺入磷组分的制备方法。Y型结晶铝硅酸盐沸石可通过由高岭土和另外的二氧化硅源产生高二氧化硅-氧化铝比率的Y型沸石来制备沸石的任何已知方法制备。另外的二氧化硅源可以为,例如,碱金属硅酸盐或添加的经历放热反应的高岭土或含水硅溶胶。已知的制备方法包括:使用含有高岭土和硅酸钠的反应混合物并随后用氢氧化钠处理从而形成沸石;用氢氧化钠处理经历放热反应的高岭土与偏高岭土的混合物从而形成沸石。由高岭土原料制成的沸石催化剂可商购获得,包括如上面所描述的那样由高岭土原料制成的BASF催化剂的原位产生的沸石催化剂。复合催化剂中形成的沸石的量的范围可为约30重量%至约70重量%,优选至少约40重量%。
由高岭土原料制成的市售含沸石催化剂通常已经受至少一个常规阳离子交换步骤,从而一般使碱金属含量减少至以总催化剂为基准按碱金属氧化物计算略低于1重量%。通常,进行铵阳离子交换从而减少催化剂的钠阳离子含量。然后使包括高岭土来源的基质在内的铵交换的Y型沸石与含有选自由磷酸二氢阴离子(H2PO4 -)、亚磷酸二氢阴离子(H2PO3 -)及其混合物组成的组的阴离子的介质接触,持续足以使磷与催化剂复合的时间。待掺入在催化剂中的磷的合适的量包括至少约0.5重量%,优选至少约0.7重量%,更优选约1.0重量%至2重量%,按P2O5计算,以沸石加上在由高岭土制备沸石时仍然伴随着沸石的所有基质的重量为基准。
所述阴离子来源于含磷组分,所述含磷组分选自由磷的无机酸、磷的无机酸的盐及其混合物组成的组。合适的含磷组分包括亚磷酸(H3PO3)、磷酸(H3PO4)、亚磷酸的盐、磷酸的盐及其混合物。尽管亚磷酸和磷酸的任何可溶性盐,诸如碱金属盐和铵盐都可用于提供磷酸二氢阴离子或亚磷酸二氢阴离子,但优选使用铵盐,因为使用碱金属盐时需要随后从催化剂中除去碱金属。优选地,所述阴离子为来源于磷酸一铵、磷酸二铵及其混合物的磷酸二氢阴离子。与阴离子的接触可作为至少一个接触步骤执行或者作为一系列接触执行,所述一系列接触可为一系列交替且连续的煅烧和磷酸二氢阴离子或亚磷酸二氢阴离子接触步骤。
阴离子与沸石和高岭土来源的基质的接触在约2至约8范围内的pH下适当地进行。选取pH下限是为了使沸石的结晶度损失减至最低。pH上限似乎是根据阴离子浓度的影响设定的。液体介质中的磷酸二氢阴离子或亚磷酸二氢阴离子的合适浓度的范围为约0.2重量%至约10.0重量%的阴离子。选取下限是为了在催化剂中提供所需下限的磷。处理溶液的pH可通过添加酸,诸如硝酸等来调节。尽管上限不是关键的,但是超出所陈述上限的浓度将不是必要的。所选的阴离子在溶液中的浓度还将取决于单位重量的被处理的沸石和基质所使用的溶液的量。处理时间和温度不是关键的,并且可以在约环境温度,即60°F至约250°F的范围内。
继加入含磷化合物之后,然后使催化剂与如本领域中已知的稀土可溶性盐水溶液的稀土阳离子进行交换。稀土化合物的实例为镧、铈、镨、钕等的硝酸盐。稀土化合物的其他水溶性盐是本领域中已知的并且可以利用这些水溶性盐。通常,加入到催化剂中的稀土的量的范围按稀土氧化物计为约0.5%至10%,通常0.5-5wt.%REO。一般来说,浸渍溶液的温度范围在约2-5的pH下为约70-200°F。尽管稀土交换在上面被描述为在第一次磷加入之后进行,但是稀土交换可以以与上面描述的顺序不同的顺序进行。例如,稀土交换可在第一次铵交换之后和磷处理之前立即进行。
继稀土交换之后,然后将稀土交换的催化剂干燥并然后在800°-1200°F的温度下煅烧。煅烧条件使得沸石晶体的单胞尺寸不显著减小。通常,在稀土交换之后的干燥步骤是为了除去包含在催化剂内的相当一大部分的水,并且在不存在添加的蒸汽的情况下进行煅烧。继煅烧之后,现进一步通常用铵离子对含稀土氧化物的催化剂进行酸交换,从而再次将钠含量减少至小于约0.5wt.%Na2O。可以重复铵交换以确保将钠含量减少至小于0.5wt.%N2O。通常,钠含量按Na2O计将被减少至低于0.2wt.%。继铵交换之后,再次使含有Y型沸石和高岭土来源的基质的钠减少的催化剂与如上面针对第一次磷处理描述的含有磷化合物的介质接触。所述介质含有足够的磷,以提供相对于包括沸石和高岭土来源的基质在内的催化剂按P2O5计至少2.0wt.%的磷含量,更通常,相对于包括沸石和高岭土来源的基质在内的催化剂按P2O5计2.8wt.%至3.5wt.%的磷量。第二次磷处理的温度和pH条件如同上面描述的第一次处理。在磷处理之后,将浸渍的催化剂在700°-1500°F的温度下再次煅烧。在这个第二次煅烧期间,在氧化气氛中可以包括一些蒸汽,至多约25%的蒸汽,以减小沸石晶体的晶胞尺寸。一般来说,结晶后未处理的(as crystalized)沸石将具有至的单胞尺寸。在第一次煅烧之后,单胞尺寸仍然在所陈述的范围内。在第二次煅烧之后,沸石的单胞尺寸可减小至低于
实施例1:(微球制备)
制备含有37.5份LHT含水高岭粘土、62.5份M-93富铝红柱石态煅烧高岭土粉末的微球。向这种含水高岭土与煅烧高岭土的混合物中加入8份从N-brandTM硅酸钠加入的SiO2。所述水合高岭土源为LHT的60%固体浆料,所述LHT,即,使所谓灰色高岭粘土离心至90重量%的颗粒的粒径小于1微米所得的粗糙副产品。将所述浆料送入喷雾干燥器中从而形成微球。煅烧微球从而使含水高岭土转化为偏高岭土,但是没有达到特征性放热。Na2O含量为3.06wt.%,酸可溶物为18.5wt.%,APS为85m,ABD为0.55gm/cc,介于40与20,000A直径之间的Hg孔隙容积为0.720gm/cc。它是商业上制备的微球MS65。
实施例2:(结晶)
通过常规程序(US4493902和US5395809)在14小时内使实施例1结晶从而形成Y型沸石。晶种描述在US4631262中。在结晶过程中止后,通过过滤将ucs为的含有~55%Y型八面沸石和~45%基质的微球从它们的相当大一部分母液中分离出来。在过滤步骤之后用水洗涤微球。洗涤步骤的目的在于除去否则将夹带在微球中的母液。结晶后未处理(as-crystallized)和经洗涤的催化剂的特性如下。
表I:钠形式催化剂的组合物
实施例3:(氨交换)
然后在搅拌的同时将实施例2加入到180°F的pH为3-3.5的27wt%硝酸铵溶液中,并逐滴加入50%HNO3以控制pH。在所有催化剂加入之后,将浆料搅拌30min,过滤,并用2倍于催化剂干重量的去离子水洗涤滤饼。完成两次此类交换,其中催化剂与27wt.%硝酸铵的重量比为1∶2。此时Na2O含量为2.09%。
比较实施例4:
在搅拌的同时将600克实施例3(以不含挥发物的重量计)加入到180°F的pH为3-3.5的含有1200g D.I.水和19g磷酸二铵(ACS级,98%)的溶液中,并逐滴加入50wt.%HNO3以控制pH。在所有催化剂加入之后,将浆料搅拌30min,过滤,并用2倍于催化剂干重量的去离子水洗涤滤饼。此时P2O5含量为1.75wt.%。然后在180°F下在3-3.5的pH下对样品进行稀土交换从而在催化剂上产生约1.36wt.%La2O3。干燥样品,并且用盖上的二氧化硅托盘在预热炉中在最初含有25wt.%水分的条件下于950°F下煅烧2小时。在煅烧之后,重复铵交换程序三次,然后在25wt.%水分和1050°F下再次煅烧从而形成成品产品。它的特性在下表II中给出。
实施例5:(本发明)
在搅拌的同时将600克实施例3(以不含挥发物的重量计)加入到180°F的pH为3-3.5的含有1200g D.I.水和19g磷酸二铵(ACS级,98%)的溶液中,并逐滴加入50wt.%HNO3以控制pH。在所有催化剂加入之后,将浆料搅拌30min,过滤,并用2倍于催化剂干重量的去离子水洗涤滤饼。此时P2O5含量为1.75wt.%。然后在180°F下在3-3.5的pH下对样品进行稀土交换从而在催化剂上产生约1.36wt.%La2O3。将样品干燥,并且用盖上的二氧化硅托盘在预热炉中在不存在添加的蒸汽的情况下于950°F下煅烧2小时。在煅烧后,重复铵交换程序五次。在搅拌的同时将所得样品加入到180°F的pH为3-3.5的含有1200g D.I.水和19g磷酸二铵(ACS级,98%)的溶液中,并逐滴加入50wt.%HNO3以控制pH。在所有催化剂加入之后,将浆料搅拌30min,过滤,并用2倍于催化剂干重量的去离子水洗涤滤饼。此时P2O5含量为3.56wt.%。将样品干燥,然后在不存在添加的蒸汽的情况下于1050°F下再次煅烧从而形成成品产品。它的特性在下表II中给出。
比较实施例6:
在180°F下3-3.5的pH下对200克实施例3(以不含挥发物的重量计)进行稀土交换从而在催化剂上产生约1.28wt.%La2O3。将样品干燥并用盖上的二氧化硅托盘在预热炉中在最初含有25wt.%水分的条件下于950°F下煅烧2小时。在煅烧后,重复铵交换程序三次。在搅拌的同时将所得样品加入到180°F的pH为3-3.5的含有400g D.I.水和11g磷酸二铵(ACS级,98%)的溶液中,并逐滴加入50wt.%HNO3以控制pH。在所有催化剂加入之后,将浆料搅拌30min,过滤,并用2倍于催化剂干重量的去离子水洗涤滤饼。此时P2O5含量为3.74wt.%。将样品干燥,然后在25wt.%水分和1050°F下再次煅烧从而形成成品产品。它的特性在下表III中给出。
比较实施例7:
在180°F下在3-3.5的pH下对实施例3进行稀土交换从而在催化剂上产生约1.28wt.%LaO3。将样品干燥,并且用盖上的二氧化硅托盘在预热炉中在最初含有25wt.%水分的条件下于950°F下煅烧2小时。在煅烧后,重复铵交换程序三次,然后在25wt.%水分和1050°F下再次煅烧从而形成成品产品。它的特性在下表III中给出。
成品产品和蒸汽灭活化产品的特性在下表中给出:
表II:成品FCC催化剂和蒸汽灭活化FCC催化剂的特性
催化剂活性的测量
使用2.125”注射器位置,基本上如美国专利第6,069,012号中所描述的那样使用在1000°F下运作的ACETM微尺度固定流化床单元、利用9克催化剂作为气油进料(表III)测定催化性能(表IV)。将催化剂汽提时间保持在575秒。油注射速率为1.2g/min。
表III:进料特性
表IV:活性和选择性
Claims (10)
1.一种用磷对FCC沸石催化剂进行改性的工艺,所述工艺包括:使结晶后未处理的催化剂与铵盐进行交换,以便使所述催化剂具有小于约2重量%Na2O的钠含量,用足以在所述催化剂上添加0.5重量%至2重量%P2O5的第一磷酸盐溶液处理所述铵交换的催化剂,对所述磷处理的催化剂进行铵离子交换从而得到按Na2O计钠含量小于约0.5wt.%的低钠催化剂,以及用足以在所述催化剂上提供2-4wt.%P2O5的第二磷酸盐溶液处理所述低钠催化剂。
2.如权利要求1所述的工艺,其包括继所述第一次铵离子交换之后或继所述第一次磷处理之后,使所述催化剂与稀土阳离子进行离子交换从而在所述催化剂中掺入按稀土氧化物计0.5wt.%至10wt.%的稀土。
3.如权利要求2所述的工艺,其中所述催化剂为Y型沸石。
4.如权利要求3所述的工艺,其中所述Y型沸石是由高岭土和另外的二氧化硅源原位形成。
5.如权利要求1所述的工艺,其中所述低钠催化剂的钠含量按Na2O计低于约0.2wt.%。
6.如权利要求1所述的工艺,其中在所述第二次磷处理后,相对于所述催化剂按P2O5计所述催化剂的磷含量为约2.8-3.5wt.%。
7.如权利要求3所述的工艺,其中继稀土交换之后,在煅烧条件下煅烧所述催化剂,使得所述Y型沸石的单胞尺寸不显著减小。
8.如权利要求7所述的工艺,其中所述煅烧在不存在添加的蒸汽的情况下进行。
9.如权利要求2所述的工艺,其中在所述第一次磷酸盐处理之后对所述稀土阳离子进行交换。
10.一种通过权利要求1-9所述的工艺制备的磷改性催化剂。
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US20150174559A1 (en) * | 2013-12-19 | 2015-06-25 | Basf Corporation | Phosphorus-Modified FCC Catalysts |
CN112209400B (zh) * | 2019-07-09 | 2022-08-05 | 中国石油化工股份有限公司 | 一种稀土y型分子筛及其制备方法 |
WO2021161081A1 (en) | 2020-02-10 | 2021-08-19 | Hindustan Petroleum Corporation Limited | An fcc additive composition for bottoms cracking and a process for preparation thereof |
CN116323872A (zh) * | 2020-11-04 | 2023-06-23 | 巴斯夫公司 | 包括磷稳定的mse框架型沸石的催化剂、其制备和其在流化催化应用中的用途 |
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