CN114453013B - 一种加氢脱芳烃催化剂的制法及加氢脱芳烃催化剂和应用 - Google Patents
一种加氢脱芳烃催化剂的制法及加氢脱芳烃催化剂和应用 Download PDFInfo
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- CN114453013B CN114453013B CN202011134770.7A CN202011134770A CN114453013B CN 114453013 B CN114453013 B CN 114453013B CN 202011134770 A CN202011134770 A CN 202011134770A CN 114453013 B CN114453013 B CN 114453013B
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- catalyst
- molecular sieve
- sba
- alumina
- pore volume
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 80
- 239000002808 molecular sieve Substances 0.000 claims abstract description 55
- 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 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 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 30
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
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- 229910052697 platinum Inorganic materials 0.000 claims description 24
- 239000011959 amorphous silica alumina Substances 0.000 claims description 23
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 40
- 239000008367 deionised water Substances 0.000 description 27
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- 239000004115 Sodium Silicate Substances 0.000 description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 19
- 229910052911 sodium silicate Inorganic materials 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
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- 229920002907 Guar gum Polymers 0.000 description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 description 5
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- 239000005995 Aluminium silicate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 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 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B01J29/0325—Noble metals
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- 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
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1062—Lubricating oils
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
项目 | A-S-1 | A-S-2 | A-S-3 | A-S-4 | A-S-5 |
比表面积,m2/g | 739 | 741 | 745 | 752 | 758 |
氧化铝含量,wt% | 28.87 | 41.78 | 28.87 | 41.78 | 60.24 |
孔容,mL/g | 1.16 | 1.11 | 1.10 | 1.15 | 1.14 |
B/L | 0.232 | 0.258 | 0.245 | 0.321 | 0.315 |
孔分布,% | |||||
<4nm | 12.18 | 12.03 | 12.24 | 13.35 | 12.48 |
4~15nm | 54.75 | 54.89 | 52.98 | 55.36 | 58.66 |
>15nm | 33.03 | 33.08 | 34.78 | 31.29 | 28.86 |
项目 | A-S-7 | A-S-8 | A-S-9 | A-S-10 |
比表面积,m2/g | 720 | 695 | 708 | 706 |
氧化铝含量,wt% | 4 | 8 | 13 | 17.25 |
孔容,mL/g | 0.85 | 0.78 | 1.05 | 1.04 |
B/L | 1.21 | 1.24 | 1.32 | 1.25 |
孔分布,% | ||||
<4nm | 42.69 | 46.28 | 45.36 | 42.05 |
4~15nm | 38.25 | 35.69 | 36.45 | 38.56 |
>15nm | 19.06 | 18.03 | 18.19 | 19.39 |
项目 | C-1 | C-2 | C-3 | C-4 | C-5 |
Pt,wt% | 0.18 | 0.17 | 0.19 | 0.19 | 0.18 |
Pd,wt% | 0.35 | 0.36 | 0.33 | 0.35 | 0.35 |
比表面积,m2/g | 422 | 419 | 421 | 418 | 429 |
孔容,mL/g | 0.76 | 0.74 | 0.75 | 0.74 | 0.75 |
Pt/Al | 0.557 | 0.559 | 0.558 | 0.560 | 0.562 |
Pd/Al | 0.549 | 0.552 | 0.551 | 0.552 | 0.553 |
项目 | C-6 | C-7 | C-8 | C-9 | C-10 |
Pt,wt% | 0.19 | 0.19 | 0.19 | 0.19 | 0.19 |
Pd,wt% | 0.41 | 0.41 | 0.41 | 0.41 | 0.41 |
比表面积,m2/g | 388 | 365 | 342 | 332 | 346 |
孔容,mL/g | 0.67 | 0.63 | 0.62 | 0.62 | 0.63 |
Pt/Al | 0.428 | 0.492 | 0.488 | 0.491 | 0.496 |
Pd/Al | 0.418 | 0.485 | 0.479 | 0.481 | 0.483 |
分析项目 | 低压加氢异构>320℃润滑油料 |
密度(20℃)/kg·m-3 | 857 .8 |
硫,μg/g | 3.0 |
氮,µg/g | 1.0 |
倾点, ℃ | -30 |
粘度(100℃),mm2/s | 5.137 |
粘度(40℃),mm2/s | 28.41 |
残炭,wt% | 0.01 |
芳烃,wt% | 11.7 |
催化剂编号 | C-1 | C-2 | C-3 | C-4 | C-5 |
反应温度,℃ | 217 | 217 | 217 | 217 | 217 |
体积空速,h-1 | 0.62 | 0.62 | 0.62 | 0.62 | 0.62 |
液收, wt% | 99.8 | 99.8 | 99.8 | 99.7 | 99.8 |
粘度(40℃), mm2/s | 33.5 | 33.6 | 33.5 | 33.4 | 33.3 |
粘度(100℃), mm2/s | 6.78 | 6.76 | 6.74 | 6.77 | 6.62 |
倾点, ℃ | -12 | -11 | -12 | -11 | -11 |
赛氏色度/号 | +32 | +33 | +32 | +31 | +30 |
易炭化物(100℃) | 通过 | 通过 | 通过 | 通过 | 通过 |
稠环芳烃(260~420nm)/cm | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
催化剂编号 | C-6 | C-7 | C-8 | C-9 | C-10 |
反应温度,℃ | 217 | 217 | 217 | 217 | 217 |
体积空速,h-1 | 0.62 | 0.62 | 0.62 | 0.62 | 0.62 |
液收,wt% | 97.9 | 95.2 | 96.3 | 95.8 | 97.6 |
粘度(40℃),mm2/s | 28.7 | 28.2 | 29.3 | 29.9 | 29.3 |
粘度(100℃),mm2/s | 5.55 | 5.33 | 5.85 | 5.79 | 5.81 |
倾点, ℃ | -10 | -10 | -8 | -10 | -9 |
赛氏色度/号 | +29 | +29 | +28 | +28 | +27 |
易炭化物(100℃) | 不通过 | 不通过 | 不通过 | 不通过 | 不通过 |
稠环芳烃(260~420nm)/cm | 0.2 | <0.2 | <0.3 | <0.3 | 0.3 |
无定形硅铝编号 | A1 | A2 | A3 | A5 |
比表面积,m2/g | 518 | 535 | 527 | 496 |
孔容,mL/g | 1.32 | 1.23 | 1.27 | 1.21 |
孔分布,% | ||||
4~15nm | 88 | 85 | 86 | 91 |
>15nm | 3 | 2 | 4 | 3 |
Claims (13)
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