CN110038582A - 一种加氢裂化催化剂的制法 - Google Patents
一种加氢裂化催化剂的制法 Download PDFInfo
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- CN110038582A CN110038582A CN201810037403.1A CN201810037403A CN110038582A CN 110038582 A CN110038582 A CN 110038582A CN 201810037403 A CN201810037403 A CN 201810037403A CN 110038582 A CN110038582 A CN 110038582A
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
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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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- 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
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- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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
- 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
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Abstract
Description
催化剂编号 | A | B | C | D | E | F | G | H |
催化剂组成 | ||||||||
NiO,wt% | 19 | 18 | 20 | 16 | 19 | 19 | 19 | 19 |
WO<sub>3</sub>,wt% | 28 | 32 | 33 | 36 | 28 | 28 | 28 | 28 |
SiO<sub>2</sub>,wt% | 22 | 22 | 21 | 22 | 22 | 22 | 22 | 22 |
Al<sub>2</sub>O<sub>3</sub>,wt% | 31 | 25 | 26 | 26 | 31 | 31 | 31 | 31 |
其它,wt% | - | ZrO<sub>2</sub>/3.0 | - | - | - | - | - | - |
催化剂性质 | ||||||||
比表面积,m<sup>2</sup>/g | 392 | 387 | 386 | 381 | 354 | 391 | 365 | 375 |
孔容,mL/g | 0.408 | 0.400 | 0.399 | 0.395 | 0.365 | 0.415 | 0.381 | 0.389 |
机械强度,N/mm | 19.4 | 19.7 | 19.1 | 19.6 | 17.7 | 17.8 | 17.1 | 17.3 |
孔分布,% | ||||||||
<4nm | 12.81 | 12.90 | 12.38 | 12.69 | 56.12 | 13.46 | 45.35 | 44.02 |
4nm~10nm | 65.87 | 65.46 | 65.56 | 65.74 | 30.12 | 46.08 | 38.05 | 38.39 |
10nm~15nm | 10.79 | 10.92 | 11.25 | 10.81 | 8.11 | 36.06 | 8.38 | 9.13 |
>15nm | 10.53 | 10.72 | 10.81 | 10.76 | 5.65 | 4.40 | 8.22 | 8.46 |
催化剂编号 | 平均堆积层数N<sub>A</sub> | 平均片层长度L<sub>A</sub>,nm |
A | 6.21 | 4.80 |
B | 6.14 | 4.86 |
C | 6.10 | 4.90 |
D | 6.11 | 4.85 |
E | 4.02 | 6.68 |
F | 4.18 | 6.89 |
G | 3.98 | 7.01 |
H | 4.05 | 6.92 |
催化剂编号 | A | B | C | D | E | F | G | H |
片层数分布,% | ||||||||
<3层 | 3.03 | 3.58 | 3.84 | 3.69 | 15.35 | 13.25 | 14.93 | 14.85 |
3至小于5层 | 10.54 | 11.23 | 11.15 | 11.53 | 76.25 | 75.95 | 75.09 | 75.26 |
5~7层 | 74.77 | 74.12 | 74.07 | 73.96 | 7.38 | 9.05 | 8.11 | 7.91 |
>7层 | 11.66 | 11.07 | 10.94 | 10.82 | 1.02 | 1.75 | 1.87 | 1.98 |
长度分布,% | ||||||||
<4nm | 17.88 | 17.67 | 17.74 | 17.55 | 5.69 | 5.26 | 6.08 | 4.99 |
4~6nm | 74.83 | 74.28 | 74.05 | 74.01 | 12.36 | 13.95 | 14.02 | 14.21 |
大于6至8nm | 6.12 | 6.61 | 6.89 | 6.94 | 71.25 | 72.22 | 71.94 | 72.08 |
>8nm | 1.17 | 1.44 | 1.32 | 1.50 | 10.70 | 8.57 | 7.96 | 8.72 |
项目 | 分析结果 |
密度(20℃),g/cm<sup>3</sup> | 0.9205 |
馏程范围,℃ | 314-539 |
S,µg/g | 10100 |
N,µg/g | 1920 |
残炭,wt% | 0.18 |
凝点,℃ | 33 |
催化剂编号 | A | B | C | D |
反应温度,℃ | 390 | 390 | 391 | 391 |
进料中氮含量,µg/g | 112.2 | 89.4 | 104.2 | 99.7 |
产品分布和性质,wt% | ||||
重石脑油(82~138℃) | ||||
收率,wt% | 8.4 | 8.1 | 8.6 | 8.2 |
芳潜,wt% | 53.5 | 53.4 | 53.1 | 53.0 |
喷气燃料(138℃~249℃) | ||||
收率,wt% | 28.4 | 28.1 | 28.3 | 28.3 |
烟点,mm | 32 | 33 | 31 | 32 |
柴油(249℃~371℃) | ||||
收率,wt% | 28.5 | 28.5 | 28.3 | 28.4 |
十六烷值 | 71.1 | 70.9 | 70.2 | 70.6 |
尾油(>371℃) | ||||
收率,wt% | 30.3 | 30.5 | 30.5 | 30.5 |
BMCI值 | 6.3 | 6.2 | 6.6 | 6.9 |
中油选择性,wt% | 81.6 | 81.4 | 81.4 | 81.6 |
催化剂编号 | E | F | G | H |
反应温度,℃ | 396 | 396 | 395 | 396 |
进料中氮含量,µg/g | 90.6 | 105.9 | 102.7 | 89.4 |
产品分布,wt% | ||||
重石脑油(82~138℃) | ||||
收率,wt% | 9.8 | 10.0 | 9.9 | 9.7 |
芳潜,wt% | 63.6 | 62.1 | 63.3 | 62.8 |
喷气燃料(138℃~249℃) | ||||
收率,wt% | 18.2 | 18.8 | 19.0 | 18.9 |
烟点,mm | 22 | 24 | 24 | 23 |
柴油(249℃~371℃) | ||||
收率,wt% | 20.4 | 20.2 | 19.9 | 20.1 |
十六烷值 | 61.5 | 61.9 | 60.8 | 61.1 |
尾油(>371℃) | ||||
收率,wt% | 42.0 | 42.2 | 42.1 | 42.5 |
BMCI值 | 18.5 | 20.9 | 19.1 | 21.6 |
中油选择性,wt% | 66.5 | 67.5 | 67.1 | 67.8 |
相对结晶度,% | 95 |
晶胞参数,nm | 2.439 |
SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub>,mol/mol | 12.05 |
比表面积,m<sup>2</sup>/g | 839 |
孔容,mL/g | 0.506 |
1.7~10nm二次孔占总孔容,% | 48.0 |
红外总酸,mmol/g | 0.999 |
Na<sub>2</sub>O,wt% | 0.093 |
Claims (25)
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