CN1064862C - 一种加氢裂化催化剂 - Google Patents
一种加氢裂化催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 title description 3
- 239000001257 hydrogen Substances 0.000 title description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 2
- 238000005336 cracking Methods 0.000 title description 2
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- 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 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims 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 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 12
- 239000011734 sodium Substances 0.000 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
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- 238000010835 comparative analysis Methods 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Classifications
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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
- B01J29/16—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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- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/04—Mixing
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
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Abstract
本发明涉及一种加氢裂化催化剂，该催化剂由低钠高硅Y型分子筛USSSY，耐熔无机氧化物和钨或/和钼，镍或钴组成，各组分含量(以催化剂为基准，重%)为：USSSY10～75%，耐熔无机氧化物10～60%，钨或/和钼(以氧化物计)12～30%，镍或钴(以氧化物计)3～6%。该催化剂在处理较高氮含量的进料时，仍能保持较高的活性稳定性。
Description
本发明涉及一种加氢裂化催化剂。
加氢裂化是油品轻质化的重要手段，近年来，原油变重和对轻质油品的要求增加的矛盾日益严重，这就对加氢精制、加氢裂化催化剂提出了越来越高的要求。对加氢裂化催化剂，要求具有较高的抗氮和破环能力，尤其是在中压下更希望裂化催化剂有较高的抗氮能力和开环能力。提高催化剂抗氮能力的有效途径之一，是提高分子筛组分的抗氮能力。到目前为止，分子筛抗氮能力提高的有效途径是NH4NaY分子筛经氟硅酸盐或酸处理。酸处理尽管能得到很高的抗氮能力，但最终分子筛的活性损失也较大，且酸溶液对设备腐蚀严重。
US4762813专利中介绍了一种选择性生产中间馏分油的烃转化催化剂，其中所用的沸石包括LZ-210，LZ-210的制备是在缓冲溶液存在下，用氟硅酸铵对铵钠Y沸石抽铝补硅。
US4672048专利中介绍了一种加氢裂化催化剂，该催化剂所用的结晶硅铝沸石为LZ-210交换稀土离子的LZ-210-M和LZ-210经水热处理后得到的LZ-210-T分子筛。
以上专利技术所用的LZ-210分子筛钠含量较高，要获得较低的钠含量还需进一步铵交换，另外分子筛中残留氟量较高，降低了分子筛的活性，因而会降低制得催化剂的活性和催化剂的抗氮性能。因此，制备的催化剂均要求加氢裂化原料中氮含量小于10×10-4w％，未有较高氮的评价结果和具体说明。
本发明的目的在于通过在加氢裂化催化剂中加入高抗氮的分子筛以增加催化剂的抗氮能力，从而使催化剂在馏分油加氢裂化过程中，特别是中压条件下，具有更高的活性和稳定性。
本发明催化剂是一种加氢裂化催化剂，由Y型分子筛，耐熔无机氧化物和VIB族金属钨和／或钼、Ⅷ族金属镍或钴组成，其中，所说的Y型分筛是一种按中国专利90102645．X记载的方法制备的低钠高硅Y型分子筛再经500～600℃水热处理后得到。低钠高硅Y型分子筛制备方法是NH4NaY分子筛用氟硅酸铵水溶液处理后与含氟副产物分离，得到的低钠高硅分子筛SSY，其Na2O含量低于0．2w％、SiO2／Al2O3摩尔比6～40、晶胞常数2．440～2．460nm，SSY经500～600℃水热处理后得到USSSY分子筛。催化剂中含上述分子筛10～75w％、耐熔无机氧化物10～60w％、VIB族金属氧化物12～30w％、Ⅷ族金属氧化物3～6w％。
用于本发明催化剂的耐熔无机氧化物，包括氧化铝、无定型硅酸铝，或它们的混合物，其中氧化铝包括大孔氧化铝和小孔氧化铝。它们在催化剂中的组成为：大孔氧化铝0～35w％，小孔氧化铝10～25w％，无定型硅酸铝0～25w％。
本发明催化剂的制备方法是：
(1)按CN90102645．X的方法制备低钠高硅Y型分子筛SSY，在0．05～0．2MPa的水分压下500～600℃处理0．5～2小时，制得超
稳高硅Y型分子筛USSSY。
(2)在小孔Al2O3中，加入稀硝酸研成胶状物，制得粘合剂。
(3)将(1)制得的分子筛，(2)制得的粘合剂或／和大孔Al2O3无定型硅酸铝，加氢金属钨和／或钼、镍盐混合成型，干燥，焙烧制成催化剂。
或者采用：
将(1)制得的分子筛，(2)制得的粘合剂和／或大孔Al2O3无定型硅酸铝混合，挤条，干燥，焙烧制成担体，用含钨镍的混合溶液浸渍、干燥、焙烧制成催化剂。
按CN90102645．X的方法制备的低钠高硅分子筛，其晶胞常数为2．449～2．453nm，结晶度一般大于95％，经水热处理后，制得的USSSY分子筛晶胞常数2．436～2．444nm，相对结晶度大于80％，SiO2／Al2O3摩尔比6～40，Na2O含量≤0．2w％。
本发明所用的大孔Al2O3，孔容为0．8～1．1ml／g，表面积230～400m2／g。三水氧化铝含量为＜2w％，小孔Al2O3的孔容为0．4～0．6ml／g，表面积180～340m2／g，三水氧化铝含量＜3w％，无定型硅酸铝的SiO2含量10～90w％，孔容0．56～1．08ml／g，比表面积220～360m2／g。
催化剂中加氢金属为元素周期表中VIB族的钨或／和钼，Ⅷ族的镍或钴。其加入方式可以是直接用金属氧化物，如三氧化钼和／或三氧化钨、硝酸镍或碳酸镍与分子筛，耐熔无机氧化物，粘合剂机械混合，也可以用无机盐，如偏钨酸铵、钨酸、钼酸铵，硝酸镍、硝酸钴、镍或钴的碳酸盐等配成溶液，对由分子筛，耐熔无机氧化物和粘合剂制成的担体进行浸渍。
现在，工业上普遍使用的催化剂都要求原料油氮含量小于10×10-4w％，本发明由于采用高活性和高抗氮性能的特殊分子筛，用由其制备的催化剂，在反应活性不降低的前题下，允许原料油氮在30×10-4w％左右，且活性稳定性好。
下面通过实例进一步描述本发明：
例1
按中国专利90102645．X记载的方法制备低钠高硅分子筛SSY，把SSY在0．1MPa、600℃水蒸汽下处理1小时，得到USSSY-1，
例2
把例1中制备的SSY在0．05MPa、500℃水蒸汽下处理1小时，得到USSSY-2。
例3
把例1中制备的SSY在0．2MPa、550℃水蒸汽下处理1小时，得到USSSY-3。
例1～例3制备的USSSY性质列于表1：
例4
将USSSY-1180．5克，H2WO4 100．8克，Ni(NO3)2·6H2O 82．8克，由75．4克小孔Al2O3(孔容0．47ml／g，比表面280m2／g)中加入0．2N稀HNO3440ml研糊制得的粘合剂(后面例中所用粘合剂制备方法与此相同)，一同放入碾压机中，碾成可挤糊膏，挤条，阴干，110℃干燥，空气流中500℃焙烧，制得催化剂A。
表1
例5
将USSSY-2 80．8克，大孔Al2O3(表面积350m2／g，孔容0．90ml／g)40．7克，无定型硅酸铝(孔容0．64ml／g，表面积310m2／g)47．5克，粘合剂105．5克，一同放入碾压机中，碾压成可挤条糊膏，挤条，干燥，600℃焙烧，制得的载体用偏钨酸铵，硝酸镍混合水溶液浸渍，干燥，500℃焙烧，制得催化剂B。
例6
将USSSY-3 40．9克，大孔Al2O3 88．2克(孔容0．90ml／g，表面积350m2／g)，H2WO4 105．0g，Ni(NO3)2．6H2O 88．2g，粘合剂220．5克，挤条成型，110℃干燥，500℃焙烧，制得催化剂C。例4～例6催化剂的组成列于表2：
表2
| 催化剂 | A | B | C |
| 组成，W％USSSY小孔Al2O3大孔Al2O3无定型硅铝WO3NiO | 48．820．4- -- -25．15．6 | 28．614．411．216．824．14．9 | 13．021．028．0- -31．07．0 |
例7
本例为比较催化剂，15gMoO3，20g Ni(NO3)2·6H2O，59．9gUSY分子筛，66．7g小孔Al2O3制得的粘合剂，在碾压机内碾成可挤糊膏，挤条，干燥，500℃焙烧，制得的催化剂E组成为：MoO3 15％，NiO 5％，USY 6O％，小孔Al2O3 20％。催化剂相对活性评价：
催化剂的评价采用一段串联一次通过流程，减压馏分油首先用加氢精制反应脱除杂原子和芳烃部分加氢，将氮、硫脱至一定程度，另外补加一定浓度的CS2，使硫含量在原料中维持0．3w％，做为本发明所用的原料，评价所用的原料油性质如下：
表3
(1)A和E对比评价：
使用原料一，进行催化剂A和E的活性对比评价，工艺条件和评价结果如表4：
表4
从表4可以看出，在相同的反应温度下，本发明催化剂A具有更高活性和抗氮能力，而且本发明催化剂产气少，石脑油芳潜高。(2)催化剂A在不同反应压力下的活性评价：
使用原料二，在不同压力下用催化剂A进行评价试验，结果如表5。
表5 催化剂A不同压力下的评价结果
从表5可以看出，在中压情况下，原料油氮含量较高时，仍然能生产合格产品。
(3)催化剂A、B、C活性对比评价：
使用原料二，在相同工艺条件(氢分压14．7MPa，氢油体积比1500∶1，空速1．5h-1)，A、B、C三种催化剂评价结果如表6。
表6
从表6可以看出用本发明的催化剂针对不同的操作方式均具有较高的活性，而且可生产出合格产品。
(4)活性稳定性试验：
使用原料1，在7．8MPa下，用催化剂A，控制原料油中氮含量在2 0～30×10-4w％，进行2100小时稳定性试验，当＜320℃转化率保持60w％不变的情况下，反应温度仅提高3℃，升温速度为0．034℃／d，证明本发明催化剂在氮含量很高时，仍具有较高的活性稳定性。
Claims (2)
1、一种加氢裂化催化剂，由10～75w％Y型分子筛、10～60w％耐熔无机氧化物、12～30w％钨和／或钼的氧化物、3～6w％镍或钴的氧化物组成，其特征在于，所说的Y型分子筛是一种经500～600℃高温水热处理、Na2O含量低于0．2w％的高硅Y型分子筛USSSY，所说的耐熔无机氧化物是氧化铝、氧化硅、无定形硅酸铝或它们的混合物。
2、按照权利要求1所述的催化剂，其特征在于所说的USSSY分子筛是NH4NaY分子筛经氟硅酸铵水溶液处理得到的低钠高硅分子筛SSY再经500～600℃高温水热处理得到的，其Na2O含量低于0．2w％，SiO2／Al2O3摩尔比6～40，晶胞常数2. 436～2. 444nm。
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| Application Number | Priority Date | Filing Date | Title |
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| CN941177580A CN1064862C (zh) | 1994-11-09 | 1994-11-09 | 一种加氢裂化催化剂 |
| US08/554,886 US6043178A (en) | 1994-11-09 | 1995-11-09 | Midbarrel hydrocracking catalyst and preparation thereof |
| KR1019950040486A KR100348430B1 (ko) | 1994-11-09 | 1995-11-09 | 미드배럴하이드로크래킹촉매및그의제조방법 |
| JP29153195A JP3311219B2 (ja) | 1994-11-09 | 1995-11-09 | 水素添加分解触媒とその製造方法 |
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| CN941177580A CN1064862C (zh) | 1994-11-09 | 1994-11-09 | 一种加氢裂化催化剂 |
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| CN1064862C true CN1064862C (zh) | 2001-04-25 |
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| Country | Link |
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| US (1) | US6043178A (zh) |
| JP (1) | JP3311219B2 (zh) |
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| CN (1) | CN1064862C (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7238276B2 (en) * | 2000-05-19 | 2007-07-03 | China Petroleum Corporation | Medium-pressure hydrocracking process |
| CN1108356C (zh) * | 2000-10-26 | 2003-05-14 | 中国石油化工股份有限公司 | 一种高活性高中油性加氢裂化催化剂及其制备方法 |
| US7745372B2 (en) | 2003-12-22 | 2010-06-29 | China Petroleum & Chemical Corporation | Catalyst for selective hydrogenation of olefins and its preparation as well as use |
| US7611689B2 (en) * | 2004-09-24 | 2009-11-03 | Shell Oil Company | Faujasite zeolite, its preparation and use in hydrocracking |
| CN1872962B (zh) * | 2005-05-31 | 2011-04-20 | 中国石油化工股份有限公司 | 一种含分子筛的加氢处理催化剂及其制备方法 |
| EP1880760A4 (en) | 2005-04-21 | 2010-10-06 | China Petroleum & Chemical | HYDROGENATION CATALYST AND ITS APPLICATION |
| CN100417713C (zh) * | 2006-05-23 | 2008-09-10 | 中国科学院山西煤炭化学研究所 | 用于费托合成重质蜡的加氢裂解催化剂及其制法和应用 |
| ES2303449B1 (es) * | 2006-08-01 | 2009-06-22 | Universidad Politecnica De Valencia | Hidrocraqueo de compuestos organicos utilizando la zeolita itq-33. |
| CN101724454B (zh) * | 2008-10-28 | 2015-02-18 | 中国石油化工股份有限公司 | 一种生产高辛烷值汽油的加氢裂化方法 |
| CN101722014B (zh) * | 2008-10-28 | 2011-06-22 | 中国石油化工股份有限公司 | 加氢脱硫催化剂及其制备方法和应用 |
| CN101992119B (zh) * | 2009-08-31 | 2013-04-03 | 中国石油化工股份有限公司 | 用于丁烯和乙烯制丙烯的催化剂及其制备方法 |
| CN103769200B (zh) * | 2012-10-24 | 2015-09-30 | 中国石油化工股份有限公司 | 一种制备硫化型加氢裂化催化剂的方法 |
| CN103769198B (zh) * | 2012-10-24 | 2015-09-30 | 中国石油化工股份有限公司 | 一种硫化型加氢裂化催化剂的制备方法 |
| CN103301872B (zh) * | 2013-07-11 | 2015-08-05 | 中科合成油内蒙古有限公司 | 一种非硫化态催化剂及其制备方法与应用 |
| CN103521260B (zh) * | 2013-10-18 | 2015-04-08 | 中国石油天然气集团公司 | 一种含有Ti-P-Beta分子筛的加氢裂化催化剂及其制备方法 |
| CN103521255B (zh) * | 2013-10-18 | 2015-02-04 | 中国石油天然气集团公司 | 一种含有Ti-P-Y分子筛的加氢裂化催化剂及其制备方法 |
| CN111097491B (zh) * | 2018-10-26 | 2021-05-14 | 中国石油化工股份有限公司 | 含高硅分子筛的加氢裂化催化剂及其制备方法和应用 |
| WO2020119754A1 (zh) | 2018-12-13 | 2020-06-18 | 中国石油化工股份有限公司 | 一种加氢裂化催化剂及其制备方法和应用 |
| CN112691692A (zh) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | 加氢裂化催化剂载体及其制备方法 |
| CN112723372B (zh) * | 2019-10-28 | 2022-08-12 | 中国石油化工股份有限公司 | 一种富含中强酸的改性y型分子筛及其制备方法与应用 |
| CN114433174B (zh) * | 2020-10-19 | 2024-05-07 | 中国石油化工股份有限公司 | 一种硅铝载体及其制备方法和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3929620A (en) * | 1974-12-04 | 1975-12-30 | Grace W R & Co | Hydrocracking catalyst and process |
| CA1037456A (en) * | 1974-01-14 | 1978-08-29 | W.R. Grace And Co. | Hydrocracking catalyst and process |
| US4672048A (en) * | 1979-10-15 | 1987-06-09 | Union Oil Company Of California | Hydrocracking catalyst |
| CN1053256A (zh) * | 1989-02-28 | 1991-07-24 | 美国环球油品公司 | 使用低酸度y型沸石的中间馏分加氢裂化催化剂 |
| CN1026313C (zh) * | 1990-05-16 | 1994-10-26 | 中国石油化工总公司抚顺石油化工研究院 | 一种低钠高硅y形分子筛的制备方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4010116A (en) * | 1974-10-15 | 1977-03-01 | Filtrol Corporation | Fluid cracking catalysts |
| US4762813A (en) * | 1979-10-15 | 1988-08-09 | Union Oil Company Of California | Hydrocarbon conversion catalyst |
| US4517033A (en) * | 1982-11-01 | 1985-05-14 | Mitsubishi Denki Kabushiki Kaisha | Contact material for vacuum circuit breaker |
| US4735928A (en) * | 1983-05-02 | 1988-04-05 | Union Carbide Corporation | Hydrocracking catalyst |
| TW252053B (zh) * | 1991-11-01 | 1995-07-21 | Shell Internat Res Schappej Bv |
-
1994
- 1994-11-09 CN CN941177580A patent/CN1064862C/zh not_active Expired - Lifetime
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- 1995-11-09 KR KR1019950040486A patent/KR100348430B1/ko not_active IP Right Cessation
- 1995-11-09 US US08/554,886 patent/US6043178A/en not_active Expired - Lifetime
- 1995-11-09 JP JP29153195A patent/JP3311219B2/ja not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1037456A (en) * | 1974-01-14 | 1978-08-29 | W.R. Grace And Co. | Hydrocracking catalyst and process |
| US3929620A (en) * | 1974-12-04 | 1975-12-30 | Grace W R & Co | Hydrocracking catalyst and process |
| US4672048A (en) * | 1979-10-15 | 1987-06-09 | Union Oil Company Of California | Hydrocracking catalyst |
| CN1053256A (zh) * | 1989-02-28 | 1991-07-24 | 美国环球油品公司 | 使用低酸度y型沸石的中间馏分加氢裂化催化剂 |
| CN1026313C (zh) * | 1990-05-16 | 1994-10-26 | 中国石油化工总公司抚顺石油化工研究院 | 一种低钠高硅y形分子筛的制备方法 |
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| Publication number | Publication date |
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| KR960016962A (ko) | 1996-06-17 |
| JPH08252460A (ja) | 1996-10-01 |
| CN1174755A (zh) | 1998-03-04 |
| JP3311219B2 (ja) | 2002-08-05 |
| US6043178A (en) | 2000-03-28 |
| KR100348430B1 (ko) | 2002-12-16 |
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