CN115518663B - 一种渣油加氢裂化催化剂的制备方法 - Google Patents
一种渣油加氢裂化催化剂的制备方法 Download PDFInfo
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- CN115518663B CN115518663B CN202110708852.6A CN202110708852A CN115518663B CN 115518663 B CN115518663 B CN 115518663B CN 202110708852 A CN202110708852 A CN 202110708852A CN 115518663 B CN115518663 B CN 115518663B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012266 salt solution Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000004898 kneading Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract 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 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 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 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 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
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 235000010981 methylcellulose Nutrition 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 abstract description 5
- 230000023556 desulfurization Effects 0.000 abstract description 5
- 239000002283 diesel fuel Substances 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- 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
-
- 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
- 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
-
- 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
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C10G45/06—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 nickel or cobalt metal, or compounds thereof
- C10G45/08—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 nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/205—Metal content
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
Description
反应条件 | |
温度,℃ | 405 |
压力,MPa, | 15 |
空速,h-1 | 0.1 |
氢油体积比 | 700 |
原料 | 中东渣油 |
S,wt% | 3.1 |
Ni,µg/g | 35.6 |
V,µg/g | 60.0 |
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | 比较例2 | 比较例3 | |
催化剂编号 | A | B | C | D | E | F | G | H |
比表面积,m2/g | 214 | 209 | 203 | 198 | 200 | 145 | 112 | 163 |
孔容,mL/g | 0.85 | 0.82 | 0.86 | 0.81 | 0.82 | 0.68 | 0.72 | 0.75 |
可几孔径,nm | 17 | 17 | 17 | 20 | 17 | 17 | 22 | 20 |
MoO3,% | 16.5 | 16.5 | 16.3 | 16.7 | 16.5 | 16.4 | 16.2 | 16.3 |
NiO,% | 4.1 | 4.0 | 4.1 | 4.2 | 4.1 | 4.2 | 4.1 | 4.2 |
酸性质 | ||||||||
150-250℃,mL/g | 6.691 | 6.576 | 6.676 | 6.137 | 6.376 | 5.250 | 5.651 | 5.841 |
250-400℃,mL/g | 3.277 | 3.229 | 3.212 | 2.896 | 3.112 | 2.574 | 2.171 | 2.651 |
400-500℃,mL/g | 1.062 | 1.062 | 1.042 | 0.972 | 0.996 | 0.573 | 0.473 | 0.481 |
总酸量,mL/g | 11.03 | 10.867 | 10.93 | 10.005 | 10.484 | 8.397 | 8.295 | 8.973 |
评价试验结果 | ||||||||
脱硫率,wt% | 89.6 | 89.4 | 89.3 | 88.6 | 89.1 | 83.2 | 79.5 | 85.2 |
脱金属率,wt% | 95.2 | 96.3 | 95.8 | 97.5 | 95.6 | 90.5 | 91.2 | 92.5 |
柴油收率,wt% | 14.5 | 14.2 | 15..2 | 13.8 | 14.6 | 8.5 | 7.9 | 9.1 |
Claims (8)
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Publication number | Priority date | Publication date | Assignee | Title |
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CN1952055A (zh) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | 一种烃类加氢处理催化剂的制备方法 |
WO2014071686A1 (zh) * | 2012-11-08 | 2014-05-15 | 中国石油化工股份有限公司 | 一种加氢处理催化剂,其制造方法及其应用 |
CN103801312A (zh) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | 一种加氢处理催化剂的制备方法 |
CN103801346A (zh) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | 一种制备加氢处理催化剂的方法 |
CN104587993A (zh) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | 一种加氢精制催化剂的制备方法 |
WO2018019203A1 (zh) * | 2016-07-29 | 2018-02-01 | 武汉凯迪工程技术研究总院有限公司 | 高负载量硼改性加氢精制催化剂及其制备方法 |
CN111821993A (zh) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | 一种重油加氢脱金属催化剂的制备方法 |
CN112694109A (zh) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | 一种拟薄水铝石的制备方法 |
CN112742425A (zh) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | 一种加氢催化剂及其制备方法 |
-
2021
- 2021-06-25 CN CN202110708852.6A patent/CN115518663B/zh active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1952055A (zh) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | 一种烃类加氢处理催化剂的制备方法 |
WO2014071686A1 (zh) * | 2012-11-08 | 2014-05-15 | 中国石油化工股份有限公司 | 一种加氢处理催化剂,其制造方法及其应用 |
CN103801312A (zh) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | 一种加氢处理催化剂的制备方法 |
CN103801346A (zh) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | 一种制备加氢处理催化剂的方法 |
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WO2018019203A1 (zh) * | 2016-07-29 | 2018-02-01 | 武汉凯迪工程技术研究总院有限公司 | 高负载量硼改性加氢精制催化剂及其制备方法 |
CN111821993A (zh) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | 一种重油加氢脱金属催化剂的制备方法 |
CN112694109A (zh) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | 一种拟薄水铝石的制备方法 |
CN112742425A (zh) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | 一种加氢催化剂及其制备方法 |
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