CN107051575B - 优化型柴油加氢裂化催化剂及其制备方法 - Google Patents
优化型柴油加氢裂化催化剂及其制备方法 Download PDFInfo
- Publication number
- CN107051575B CN107051575B CN201710264309.5A CN201710264309A CN107051575B CN 107051575 B CN107051575 B CN 107051575B CN 201710264309 A CN201710264309 A CN 201710264309A CN 107051575 B CN107051575 B CN 107051575B
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- Prior art keywords
- molecular sieve
- modified
- catalyst
- hydrocracking catalyst
- aluminum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000002808 molecular sieve Substances 0.000 claims abstract description 62
- 238000001035 drying Methods 0.000 claims abstract description 23
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 23
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 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 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 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 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 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
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- B01J35/615—
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- 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
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
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- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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Abstract
本发明公开了一种优化型柴油加氢裂化催化剂及其制备方法,原料包括以下组分及重量百分比:1~25%的改性分子筛,10~65%的γ‑Al2O3,15~70%的无定形硅铝,9~40%的粘结剂及10~35%的活性金属氧化物;所述催化剂的比表面积为200~400m2/g,总孔容为0.30~0.65cm3/g。本发明载体在制备γ‑Al2O3的无机铝盐溶液中加入改性分子筛,经沉淀、干燥、焙烧,得到分子筛与γ‑Al2O3的复合材料,然后照催化剂的物料比例,将其余物料与复合材料进行混合、碾压、成型、干燥、活化得到催化剂,本发明催化剂的催化剂载体中分子筛具有高硅铝比,大比表面积且在载体中分散度高,使载体具有更加均匀的酸性位,氧化铝与分子筛接触的更加紧密,使得本催化剂可在保证柴油高收率的前提下,明显地降低柴油馏分的凝点,提高柴油的十六烷值。
Description
技术领域
本发明涉及催化剂,具体地指一种优化型柴油加氢裂化催化剂及其制备方法。
背景技术
加氢裂化作为炼油工业非常重要的重质油高效转化和清洁油品生产的技术,可加工高硫、高金属的重质原油,具有原料来源广,生产灵活性大,产品质量好及中间馏分油收率高等特点。加氢裂化技术可以从减压柴油(VGO)直接生产低芳烃,低硫及低氮的高品质中间馏分油产品,可以满足日益严格的环保要求,而催化剂在加氢裂化反应中起核心作用,加氢裂化技术的关键在于催化剂的研制和改进。
加氢裂化催化剂常规的制备方法主要有浸渍法,共沉淀法及混捏法等,其中混捏法的制备工艺最简单,对工艺及催化剂配料的要求都不高,但由于其制备过程较粗放,催化剂中各组分的分散性不好,部分金属加氢活性中心被覆盖,不能更好的发挥其活性,通常为加氢性能要求不是很高的催化剂所采用;共沉淀法制备技术制备过程最为复杂,但催化剂中各组分的分散度很好,各组分之间的匹配关系好,加氢和裂化活性中心在催化剂中均匀分布,使催化剂加氢与裂化活性中心具有更高的协同作用;浸渍法是制备加氢裂化催化剂最广泛的使用方法,首先制备出符合催化剂性能要求的载体,如载体的形状、机械强度、比表面和酸性等,然后通过饱和或过饱和浸渍方法进行负载金属组分,金属组分富集于催化剂中,使催化剂具有更高的机械强度,充分发挥其加氢性能。
然而,现有方法制得的加氢裂化催化剂,其组分之间都是简单的机械混合,催化剂中各组分容易团聚为二次粒子,使得活性组分分散性较差,制备的催化剂难以发挥最佳性能,而且还存在制备流程复杂,成本高的问题。如:CN98114489.6公开了一种加氢裂化催化剂,无定形硅铝及Y型分子筛作为裂化组分,第VIB族及第VIII族族金属氧化物为加氢组分,采用一段串联加氢裂化生产中间馏分油,该催化剂具有很好的抗氮性,但其制备方法较为复杂,制备成本较高。CN139352IA公开了一种中油型加氢裂化催化剂及其制备方法,催化剂所用载体为无定形硅铝、氧化铝和Y和β的复合型分子筛,其中复合分子筛是将β分子筛原粉烧去模板剂后与改性Y分子筛混合后,再进行铵交换处理而得,该催化剂的催化活性不高,航煤和柴油的中间馏分油的产品质量一般,需进一步提高。CN1351121A公布了一种含改性β分子筛和无定型硅铝的加氢裂化催化剂及其制备方法,该方法中改性β分子筛是将合成后的分子筛浆液直接进行铵交换,然后焙烧脱铵,酸处理和水热处理得到改性β分子筛,由于大量非骨架铝滞留在分子筛孔道中,影响了改性分子筛的酸性及其扩散性能,最终影响了柴油产品的产率和性质。
发明内容
本发明的目的就是要提供一种优化型柴油加氢裂化催化剂及其制备方法,该催化剂能在保证柴油收率的前提下,明显降低柴油馏分的凝点,并提高柴油的十六烷值。
为实现上述目的,本发明采用的技术方案是:一种优化型柴油加氢裂化催化剂,所述催化剂原料包括以下组分及其重量百分比:1~25%的改性分子筛,10~65%的γ-Al2O3,15~70%的无定形硅铝,9~40%的粘结剂及10~35%的活性金属氧化物;所述催化剂的比表面积为200~400m2/g,总孔容为0.30~0.65cm3/g。
进一步地,所述催化剂原料包括以下组分及其重量百分比:3.3~5.4%的改性分子筛,21.6~27%的γ-Al2O3,29.7~35%的无定形硅铝,15~25%的粘结剂及20~28%的活性金属氧化物;所述催化剂的比表面积为341~375m2/g,总孔容为0.49~0.57cm3/g;所述催化剂呈柱状,长度为3~8mm。
进一步地,所述改性分子筛为改性β分子筛、改性Y型分子筛、改性MOR分子筛、改性ZSM-5分子筛、改性ZSM-22分子筛及改性ZSM-23分子筛中的一种或几种。
进一步地,所述活性金属氧化物中的活性金属为W、Mo、Ni和Co的一种或几种。
进一步地,所述改性β分子筛比表面积为450~750m2/g,总孔容为0.3~0.5cm3/g。
进一步地,所述改性Y型分子筛比表面积为750~860m2/g,总孔容为0.35~0.55cm3/g。
更进一步地,所述改性MOR分子筛比表面积为300~560m2/g,总孔容为0.3~0.45cm3/g。
一种上述优化型柴油加氢裂化催化剂的制备方法,包括以下步骤:
1)水热合成法制备改性分子筛:将四乙基溴化铵溶液、氢氧化钠、铝源和水混合并搅拌至澄清溶液,然后加入硅源,继续搅拌得到硅铝凝胶;所述硅源、铝源、氢氧化钠、四乙基溴化铵溶液及水按配料摩尔比SiO2∶Al2O3∶Na2O∶四乙基溴化铵∶H2O为50~70∶1∶5~8∶15~20∶1000~1200的比例加入;接着,将硅铝凝胶进行晶化和提纯,再进行焙烧脱模板处理,得分子筛;然后,将脱完模板后的分子筛依次进行铵交换、水热处理和铝盐处理,得到改性分子筛;
2)制备改性分子筛与γ-Al2O3复合材料:将步骤1)所得改性分子筛加入铝盐和碱的混合溶液中进行沉淀,充分沉淀后取浆液依次进行干燥和焙烧处理,得改性分子筛与γ-Al2O3复合材料;
3)制备催化剂:将改性分子筛与γ-Al2O3复合材料、无定形硅铝、粘结剂及活性金属氧化物按所述原料比例进行混合,依次碾压、成型、干燥及活化,即可得所述加氢裂化催化剂。
进一步地,所述步骤1)中,铵交换条件为:温度为60~90℃,所用铵盐为0.4~0.6mol/L的氯化铵或硝酸铵。
进一步地,所述步骤1)中,水热处理条件为:温度为630~750℃,处理时间为1~4小时,表压为0.05~0.4MPa。
进一步地,所述步骤1)中,铝盐处理条件为:所用铝盐溶液中,Al3+浓度为0.5~1.5mol/L,铝盐与改性分子筛质量比为4~30∶1,处理温度为70~100℃,处理时间为1~5小时。
进一步地,所述步骤1)中,改性分子筛为改性β分子筛,晶化温度为135~145℃,焙烧脱模板处理条件为:以升温速率2℃/min升温至540~560℃后,焙烧7~9h。
进一步地,所述步骤1)中,铝源为拟薄水铝石、硫酸铝和偏铝酸钠中的一种或几种;硅源为白炭黑、硅溶胶和水玻璃中的一种或几种。
进一步地,所述步骤2)中,铝盐为硫酸铝、硝酸铝和氯化铝中的一种或多种;碱为草酸铵、氨水、氢氧化钠和氢氧化钾中的一种或多种。
进一步地,所述步骤2)中,沉淀过程中,控制温度为50~70℃,pH值为3~7;干燥温度为110~130℃;焙烧温度为300~600℃,焙烧时间为2~4小时。
更进一步地,所述步骤3)中,干燥温度为100~120℃,时间为18~22小时;活化温度为450~600℃,活化时间为4~6小时。
与现有技术相比,本发明具有以下优点:
其一,本发明加氢裂化催化剂,在制备γ-Al2O3的铝盐溶液中加入改性分子筛,加入沉淀剂后,使得氢氧化铝沉淀沉积并将改性分子筛包裹起来,沉淀干燥、焙烧后,能够使裂化活性组分均匀的分散到氧化铝中,与现有技术相比,本发明催化剂具有更加均匀酸性中心、适宜的酸度、大的比表面积和孔容,催化剂中氧化铝与分子筛接触的更加紧密,有利于反应物及产物分子在酸性中心与裂化中心之间的快速转移,使裂化和加氢两种活性组分之间具有更好的协同作用。
其二,本发明加氢裂化催化剂对长链烷烃、芳烃及环烷烃的长侧链烷基有适宜的裂化作用和很好的异构作用,中间馏分油选择性好,催化活性很高,可在保证柴油收率的前提下,明显地降低柴油馏分的凝点,提高柴油的十六烷值。
其三,本发明优化了加氢功能和酸性功能之间的匹配,形成强加氢功能与中酸或弱酸性功能组合,正碳离子能更多地在加氢活性中心上加氢饱和向异构化方向进行,减少了裂解产物的二次裂化。
具体实施方式
下面结合具体实施例对本发明作进一步的详细说明,便于更清楚地了解本发明,但它们不对本发明构成限定。
以下实施例中,比表面积和孔容采用低温液氮物理吸附法,硅铝摩尔比采用化学法,骨架硅铝采由NMR法测定;红外酸量,B酸量及L酸量采用吡啶吸附红外光谱法,钠含量采用等离子发射光谱法,分子筛相对结晶度采用XRD方法测定。
以下实施例中制备催化剂载体的主要步骤如下:
1)通过水热合成法制备改性β分子筛(比表面积为450~750m2/g,总孔容为0.3~0.5cm3/g),改性Y型分子筛(比表面积为750~860m2/g,总孔容为0.35~0.55cm3/g),改性MOR分子筛(比表面积为300~560m2/g,总孔容为0.3~0.45cm3/g),改性ZSM-5分子筛,改性ZSM-22分子筛及改性ZSM-23分子筛中的一种或几种,依据分子筛配料摩尔比,将模板剂或导向剂、铝盐、和水混合并搅拌至澄清溶液(其中改性Y型分子筛需要使用盐酸进行调节混合溶液的碱度),然后在搅拌下向所得的澄清溶液中加入硅源,并继续搅拌得到均匀的硅铝凝胶,最后将硅铝凝胶进行晶化(分子筛为β分子筛时,晶化温度为135~145℃,分子筛为MOR分子筛时,晶化温度为140~160℃,分子筛为Y型分子筛时,晶化温度为80~120℃),晶化结束后将所得固体产物经洗涤、离心、干燥,焙烧脱模板(焙烧条件为:以升温速率2℃/min升温至550℃后,焙烧7~9h),脱完模板的分子筛进行铵交换(温度为60~90℃,铵盐为0.4~0.6mol/L的氯化铵或硝酸铵),水热处理(温度为630~750℃,处理时间为1~4小时,表压为0.05~0.4MPa),铝盐处理(Al3+浓度为0.5~1.5mol/L,铝盐与分子筛比重4~30∶1,处理温度为70~100℃,时间为1~5小时),得到改性分子筛。
2)将铝盐溶液和碱沉淀剂混合,把上述改性分子筛加入混合溶液中,搅拌,温度控制在50~70℃,pH值控制在3~7,于50~90℃温度条件下进行蒸发,100℃干燥,将沉淀进行焙烧,温度为300~600℃,时间为2~4小时,得到改性分子筛与氧化铝复合材料。
3)最后,按催化剂的物料比例,将改性分子筛与氧化铝复合材料,无定形硅铝,活性金属氧化物及粘结剂进行混合、碾压、成型、干燥、活化得到催化剂,碾压时间为20~60分钟,挤条成柱状,长度为3~8nm,120℃干燥20小时,450~600℃下焙烧5~6小时,得到催化剂。
实施例1
称取201.3g四乙基溴化铵(工业级),27.39g氢氧化钠,7.2g拟薄水铝石(70wt%,工业级),870g水混合并搅拌至澄清溶液,然后在不断搅拌下向溶液中加入180g白炭黑(工业级),并继续搅拌以得到均匀的硅铝凝胶;将硅铝凝胶于145℃动态晶化7天,经固液分离和洗涤干燥后,在空气流中于550℃焙烧8小时,得到β分子筛,脱完模板后,使用浓度为0.5mol/L氯化铵溶液在80℃下进行铵交换2次,液固比为10∶1,水洗干燥后再进行水热处理,在水蒸汽压力0.15MPa,处理温度为600℃,处理时间为2.5小时,之后进行铝盐处理,将水热处理后的分子筛放入带有回流装置并可以密闭的烧瓶中,加入含浓度0.8mol/L硫酸铝水溶液1000ml,在95℃下恒温搅拌1.0 小时,水洗,过滤,以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中100℃干燥12小时,得到β改性分子筛,性质见表1。
称取140g草酸铵与3000ml氯化铝溶液(浓度为1.5mol/L)混合于5000ml烧杯中,将28.9g(干基98%)改性分子筛加入混合液中,恒温70℃,不断加入2mol/L的氨水直至pH值为4,于85℃下蒸发,将吸出的白色固体于100℃下干燥3小时,500℃下焙烧4小时得到分子筛与γ-Al2O3复合材料274.5g(干基93%),转化率为73%。将分子筛与γ-Al2O3的复合材料195.5g(干基93%)、无定形硅铝238.6g(干基88%)、MoO390.5g(99.1wt%)、Ni(NO3)2·6H2O(NiO,26.6wt%)116.7g、粘结剂360g(干基25%)进行混合,在轮碾机中进行碾压40分钟,碾压为可挤膏状,挤条成型,形状为柱状,长度为3~8nm,并于120℃干燥20小时,500℃下焙烧5~6小时,得到加氢裂化催化剂,编号为C-1,性质见表2。
实施例2
改性分子筛同实施例1中的β改性分子筛;分子筛与γ-Al2O3复合材料同实施例1;将复合材料195.5g(干基93%)、无定形硅铝204.5g(干基88%)、MoO3为108.5g(99.1wt%)、Ni(NO3)2·6H2O(NiO,26.6wt%)为163.4g、粘结剂360g(干基25%)进行混合,在轮碾机中进行碾压40分钟,碾压为可挤膏状,挤条成型,形状为柱状,长度为3~8nm,并于120℃干燥20小时,500℃下焙烧5~6小时,得到加氢裂化催化剂,编号为C-2,性质见表2。
实施例3
改性分子筛同实施例1中的β改性分子筛;称取140g草酸铵与3000ml氯化铝溶液(浓度为1.5mol/L)混合于5000ml烧杯中,将52.6g(干基98%)改性分子筛加入混合液中,恒温70℃,不断加入2mol/L的氨水直至pH值为4,于85℃下蒸发,将吸出的白色固体于100℃下干燥3小时,500℃下焙烧4小时得到分子筛γ-Al2O3复合材料272.8g(干基93%),转化率为72.3%。将分子筛与γ-Al2O3的复合材料173.2g(干基93%)、无定形硅铝238.6g(干基88%)、MoO3为108.5g(99.1wt%)、Ni(NO3)2·6H2O(NiO,26.6wt%)为116.7g、粘结剂360g(干基25%)进行混合,在轮碾机中进行碾压40分钟,碾压为可挤膏状,挤条成型,形状为柱状,长度为3~8nm,并于120℃干燥20小时,500℃下焙烧5~6小时,得到加氢裂化催化剂,编号为C-3,性质见表2。
实施例4
改性分子筛同实施例1中的β改性分子筛;分子筛与γ-Al2O3的复合材料同实施例3,将复合材料173.2g(干基93%)、无定形硅铝204.5g(干基88%)、MoO3为108.5g(99.1wt%)、Ni(NO3)2·6H2O(NiO,26.6wt%)为233.4g、粘结剂360g(干基25%)进行混合,在轮碾机中进行碾压40分钟,碾压为可挤膏状,挤条成型,形状为柱状,长度为3~8nm,并于120℃干燥20小时,500℃下焙烧5~6小时,得到加氢裂化催化剂,编号为C-4,性质见表2。
对比例1
对比实施例1,改性分子筛同实施例1中的β改性分子筛;将20.5g改性分子筛(干基98%)、氧化铝169.8g(干基96%)、无定形硅铝238.6g(干基88%)、MoO3为90.5g(99.1wt%)、Ni(NO3)2·6H2O(NiO,26.6wt%)为116.7g、粘结剂360g(干基25%)进行混合,在轮碾机中进行碾压40分钟,碾压为可挤膏状,挤条成型,形状为柱状,长度为3~8nm,并于120℃干燥20小时,500℃下焙烧5~6小时,得到加氢裂化催化剂,编号为C-5,性质见表2。
对比例2
对比实施例3,改性分子筛同实施例1中的β改性分子筛;将33.4g改性分子筛(干基98%)、氧化铝135.3g(干基96%)、无定形硅铝238.6g(干基88%)、MoO3为108.5g(99.1wt%)、Ni(NO3)2·6H2O (NiO,26.6wt%)为116.7g、粘结剂360g(干基25%)进行混合,在轮碾机中进行碾压40分钟,碾压为可挤膏状,挤条成型,形状为柱状,长度为3~8nm,并于120℃干燥20小时,500℃下焙烧5~6小时,得到加氢裂化催化剂,编号为C-6,性质见表2。
将实施例1和对比例1中的催化剂在固定床加氢实验装置上进行评价,评价条件为:反应总压为10MPa,氢油体积比为1000,体积空速1.0h-1,使用减压馏分油(VGO)为原料油,该原料油性质见表3。将催化剂C-1、C-5在相同的工艺条件下进行评价,评价结果见表4,从表4数据可以看出,在相同的工艺条件下,实施例1的催化剂具有更好中间馏分油选择性,且在保证柴油收率的前提下,明显地降低柴油馏分的凝点,提高柴油的十六烷值。
表1
硅铝比(Si/Al) | 34.5 |
相对结晶度,% | 103 |
比表面,m<sup>2</sup>/g | 625 |
总孔容,ml/g | 0.29 |
红外酸量,mmol/g | 0.28 |
B酸/L酸 | 0.56 |
Na<sub>2</sub>O,wt% | <0.01 |
表2
表3
原料油 | 减压馏分油 |
密度(20℃),kg/m<sup>3</sup> | 912.3 |
馏程,℃ | |
IBP/10% | 315/403 |
30%/50% | 442/461 |
70%/90% | 495/526 |
95%/EBP | 532/544 |
凝点,℃ | 32 |
氮,μg/g | 1568 |
碳,wt% | 84.53 |
氢,wt% | 11.72 |
残炭,wt% | 0.32 |
BMCI值 | 43 |
表4
Claims (14)
1.一种优化型柴油加氢裂化催化剂,其特征在于:所述催化剂原料包括以下组分及其重量百分比:1~25%的改性分子筛,10~65%的γ-Al2O3,15~70%的无定形硅铝,9~40%的粘结剂及10~35%的活性金属氧化物;所述催化剂的比表面积为200~400m2/g,总孔容为0.30~0.65cm3/g;
所述改性分子筛为改性β分子筛、改性Y型分子筛、改性MOR分子筛、改性ZSM-5分子筛、改性ZSM-22分子筛及改性ZSM-23分子筛中的一种或几种;
所述活性金属氧化物中的活性金属为W、Mo、Ni和Co的一种或几种;
所述优化型柴油加氢裂化催化剂的制备方法,包括以下步骤:
1)水热合成法制备改性分子筛:将四乙基溴化铵溶液、氢氧化钠、铝源和水混合并搅拌至澄清溶液,然后加入硅源,继续搅拌得到硅铝凝胶;所述硅源、铝源、氢氧化钠、四乙基溴化铵溶液及水按配料摩尔比SiO2∶Al2O3∶Na2O∶四乙基溴化铵∶H2O为50~70∶1∶5~8∶15~20∶1000~1200的比例加入;接着,将硅铝凝胶进行晶化和提纯,再进行焙烧脱模板处理,得分子筛;然后,将脱完模板后的分子筛依次进行铵交换、水热处理和铝盐处理,得到改性分子筛;
2)制备改性分子筛与γ-Al2O3复合材料:将步骤1)所得改性分子筛加入铝盐和碱的混合溶液中进行沉淀,充分沉淀后取浆液依次进行干燥和焙烧处理,得改性分子筛与γ-Al2O3复合材料;
3)制备催化剂:将改性分子筛与γ-Al2O3复合材料、无定形硅铝、粘结剂及活性金属氧化物按所述原料比例进行混合,依次碾压、成型、干燥及活化,即可得所述加氢裂化催化剂。
2.根据权利要求1所述优化型柴油加氢裂化催化剂,其特征在于:所述催化剂原料包括以下组分及其重量百分比:3.3~5.4%的改性分子筛,21.6~27%的γ-Al2O3,29.7~35%的无定形硅铝,15~25%的粘结剂及20~28%的活性金属氧化物;所述催化剂的比表面积为341~375m2/g,总孔容为0.49~0.57cm3/g;所述催化剂呈柱状,长度为3~8mm。
3.根据权利要求1所述优化型柴油加氢裂化催化剂,其特征在于:所述改性β分子筛比表面积为450~750m2/g,总孔容为0.3~0.5cm3/g。
4.根据权利要求1所述优化型柴油加氢裂化催化剂,其特征在于:所述改性Y型分子筛比表面积为750~860m2/g,总孔容为0.35~0.55cm3/g。
5.根据权利要求1所述优化型柴油加氢裂化催化剂,其特征在于:所述改性MOR分子筛比表面积为300~560m2/g,总孔容为0.3~0.45cm3/g。
6.一种权利要求1所述优化型柴油加氢裂化催化剂的制备方法,其特征在于:包括以下步骤:
1)水热合成法制备改性分子筛:将四乙基溴化铵溶液、氢氧化钠、铝源和水混合并搅拌至澄清溶液,然后加入硅源,继续搅拌得到硅铝凝胶;所述硅源、铝源、氢氧化钠、四乙基溴化铵溶液及水按配料摩尔比SiO2∶Al2O3∶Na2O∶四乙基溴化铵∶H2O为50~70∶1∶5~8∶15~20∶1000~1200的比例加入;接着,将硅铝凝胶进行晶化和提纯,再进行焙烧脱模板处理,得分子筛;然后,将脱完模板后的分子筛依次进行铵交换、水热处理和铝盐处理,得到改性分子筛;
2)制备改性分子筛与γ-Al2O3复合材料:将步骤1)所得改性分子筛加入铝盐和碱的混合溶液中进行沉淀,充分沉淀后取浆液依次进行干燥和焙烧处理,得改性分子筛与γ-Al2O3复合材料;
3)制备催化剂:将改性分子筛与γ-Al2O3复合材料、无定形硅铝、粘结剂及活性金属氧化物按所述原料比例进行混合,依次碾压、成型、干燥及活化,即可得所述加氢裂化催化剂。
7.根据权利要求6所述优化型柴油加氢裂化催化剂的制备方法,其特征在于:所述步骤1)中,铵交换条件为:温度为60~90℃,所用铵盐为0.4~0.6mol/L的氯化铵或硝酸铵。
8.根据权利要求6所述优化型柴油加氢裂化催化剂的制备方法,其特征在于:所述步骤1)中,水热处理条件为:温度为630~750℃,处理时间为1~4小时,表压为0.05~0.4MPa。
9.根据权利要求6所述优化型柴油加氢裂化催化剂的制备方法,其特征在于:所述步骤1)中,铝盐处理条件为:所用铝盐溶液中,Al3+浓度为0.5~1.5mol/L,铝盐与改性分子筛质量比为4~30∶1,处理温度为70~100℃,处理时间为1~5小时。
10.根据权利要求6~9中任一项所述优化型柴油加氢裂化催化剂的制备方法,其特征在于:所述步骤1)中,改性分子筛为改性β分子筛,晶化温度为135~145℃,焙烧脱模板处理条件为:以升温速率2℃/min升温至540~560℃后,焙烧7~9h。
11.根据权利要求6~9中任一项所述优化型柴油加氢裂化催化剂的制备方法,其特征在于:所述步骤1)中,铝源为拟薄水铝石、硫酸铝和偏铝酸钠中的一种或几种;硅源为白炭黑、硅溶胶和水玻璃中的一种或几种。
12.根据权利要求6~9中任一项所述优化型柴油加氢裂化催化剂的制备方法,其特征在于:所述步骤2)中,铝盐为硫酸铝、硝酸铝和氯化铝中的一种或多种;碱为草酸铵、氨水、氢氧化钠和氢氧化钾中的一种或多种。
13.根据权利要求6~9中任一项所述优化型柴油加氢裂化催化剂的制备方法,其特征在于:所述步骤2)中,沉淀过程中,控制温度为50~70℃,pH值为3~7;干燥温度为110~130℃;焙烧温度为300~600℃,焙烧时间为2~4小时。
14.根据权利要求6~9中任一项所述优化型柴油加氢裂化催化剂载体的制备方法,其特征在于:所述步骤3)中,干燥温度为100~120℃,时间为18~22小时;活化温度为450~600℃,活化时间为4~6小时。
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