CN112625773B - Preparation method of transformer oil base oil - Google Patents
Preparation method of transformer oil base oil Download PDFInfo
- Publication number
- CN112625773B CN112625773B CN201910953143.7A CN201910953143A CN112625773B CN 112625773 B CN112625773 B CN 112625773B CN 201910953143 A CN201910953143 A CN 201910953143A CN 112625773 B CN112625773 B CN 112625773B
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- catalyst
- oil
- reaction
- hydrodewaxing
- metal oxide
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- 239000003921 oil Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002199 base oil Substances 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 124
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims description 28
- 150000004706 metal oxides Chemical class 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- 238000010574 gas phase reaction Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000007670 refining Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 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 description 7
- 230000007774 longterm Effects 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- -1 VIB group metals Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- FBAZCZFUGZHBMZ-UHFFFAOYSA-O [NH4+].[Ni].[O-][N+]([O-])=O Chemical compound [NH4+].[Ni].[O-][N+]([O-])=O FBAZCZFUGZHBMZ-UHFFFAOYSA-O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- 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
- B01J29/40—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
- B01J29/44—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J29/40—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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- 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
- B01J29/40—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
- B01J29/48—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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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B01J35/615—100-500 m2/g
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- 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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- B01J35/635—0.5-1.0 ml/g
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- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- 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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Abstract
The invention discloses a preparation method of transformer oil base oil, which comprises the following steps: and (3) sequentially carrying out hydrodewaxing reaction and hydrofinishing reaction on the raw oil to obtain the transformer oil base oil. The method adopts the hydrodewaxing catalyst with a specific structure in the hydrodewaxing reaction process and combines the hydrofinishing process, so that the prepared transformer oil base oil has low pour point and low aromatic hydrocarbon content.
Description
Technical Field
The invention relates to the field of preparation of transformer oil base oil. More particularly, relates to a preparation method of transformer oil base oil.
Background
The transformer oil is liquid insulating heat conducting oil produced with mineral oil and consists of mainly base oil and additive. The properties of transformer oils are to a large extent dependent on the properties of the base oil. Its properties are related to the composition of the hydrocarbons involved.
For many years, transformer oil has been primarily produced from naphthenic base crude oil. Because the naphthenic base crude oil has less resources and the yield is insufficient to meet the requirement of transformer oil, the countries continuously develop related technologies and processes for producing the transformer oil from the paraffin base crude oil, but the yield of the paraffin base transformer is still low. The naphthenic base crude oil resources are relatively sufficient in China, and the production of the transformer oil is mainly performed on the naphthenic base crude oil. The prior process for producing the transformer oil by using the naphthenic base crude oil lubricating oil fraction mainly combines solvent refining and clay refining, and can also carry out hydrogenation deacidification treatment before the solvent refining. Therefore, it is necessary to develop a hydrogenation technology with low pour point, good color and good stability to produce transformer oil.
The production of transformer oil by a hydrogenation method generally comprises three technologies of hydrotreating, hydrodewaxing and hydrofinishing, and one, two or three of the technologies are selected according to the properties of raw materials and the requirements of target products. The main functions of the hydrotreating technology are to remove heterocyclic compounds such as sulfur, nitrogen and the like and to saturate polycyclic aromatic hydrocarbon into cycloparaffin, the hydrodewaxing technology is mainly to reduce the pour point of oil products, and the hydrofinishing is to saturate a small amount of residual aromatic hydrocarbon and improve the color and stability of products.
Hydrodewaxing means that raw materials react on the surface of a catalyst in the presence of hydrogen, wherein high pour point components such as straight-chain alkanes with high pour points, short-side alkanes, cycloalkanes with long side chains, aromatic hydrocarbons with long side chains and the like are selectively cracked into small molecules, and the small molecules are separated and removed from oil products so as to reduce the pour points (condensation points) of the oil products.
The key of the hydrodewaxing technology is the hydrodewaxing catalyst. The hydrodewaxing catalyst is a bifunctional catalyst, the metal component provides a hydrodehydrogenation active center, and the molecular sieve provides a pore structure and an acid center which are necessary for shape-selective cracking reaction.
Chinese patent CN106753555A discloses a method for preparing low-condensation-point transformer oil by high-pressure hydrogenation, which comprises the following steps: adding naphthenic base oil and hydrogenation catalyst subjected to vulcanization passivation treatment into a reaction kettle, introducing hydrogen, heating to 270-290 ℃, preserving heat for carrying out hydrocracking reaction, and carrying out gas-liquid separation after the reaction is finished to obtain a first hydrogenation reaction liquid. Separating the catalyst from the first hydrogenation reaction liquid, adding a hydrodewaxing catalyst, introducing hydrogen, heating to 300-320 ℃, preserving heat for shape-selective cracking reaction, and performing gas-liquid separation after the reaction is finished to obtain a second hydrogenation reaction liquid. And separating out the hydrodewaxing catalyst from the second reaction liquid, and adding activated clay for refining to obtain the low-freezing-point transformer oil. The method needs two times of gas-liquid separation and liquid-solid separation, has complex operation and high energy consumption, and also needs clay refining, thereby bringing the problem of clay consumption. The hydrodewaxing catalyst used in the invention takes mordenite as a carrier and nickel as an active metal component.
Chinese patent 106833740A discloses a preparation method of transformer oil base oil, which comprises the following steps: the method comprises the steps of carrying out hydrofining treatment on naphthenic base distillate oil under the action of a catalyst to obtain hydrofined produced oil, carrying out hydroisomerization on the hydrofined produced oil to obtain hydroisomerized produced oil, carrying out hydrogenation complementary refining on the hydroisomerized produced oil to obtain three-stage hydrogenated produced oil, and then carrying out atmospheric and vacuum fractionation to obtain fractions with the temperature of more than 280 ℃ as the transformer oil base oil.
Chinese patent CN102311785A discloses a method for producing lube base oil by hydrogenating naphthenic base distillate, which comprises the following steps: the naphthenic base distillate oil is used as a raw material, and a one-stage series hydrogenation process of hydrotreating, hydrodewaxing and hydrofinishing is adopted to produce the lubricating oil base oil. The hydrogenation pour point depressing catalyst has ZSM-5 molecular sieve content of 50-85 wt% and NiO or CoO content of 1.0-8.0 wt%.
Chinese patent CN1352231A discloses a hydrodewaxing catalyst and its preparation method, the catalyst uses aluminosilicate molecular sieve as matrix, adds a small amount of adhesive, extrudes into strips to form carrier, uses VIII group and VIB group metals as hydrogenation (dehydrogenation) components, and adopts high-temperature roasting mode to reduce the acid content of the catalyst. Wherein, the shape selective cracking molecular sieve is 60-90%, and the adhesive is 9-39%.
Chinese patent CN101143333A discloses a hydrodewaxing catalyst and its preparation method, which comprises mixing a compound containing a hydrogenation active component with an alumina dry gel to prepare an adhesive, then kneading and molding with a shape-selective cracking molecular sieve, drying and roasting to obtain a catalyst carrier, impregnating an impregnation liquid containing the rest active component and an auxiliary agent, and drying and roasting to obtain the hydrodewaxing catalyst, wherein the composition of the hydrodewaxing catalyst is as follows: nickel oxide content is 1-4%, molybdenum oxide or tungsten oxide content is 1-9%, shape-selective cracking molecular sieve is 60.0-75.0%, aluminium oxide is 15.0-30.0% and adjuvant is 0.2-2.0%.
However, the utilization rate of the molecular sieve in the hydrodewaxing catalyst in the above patent is low, the catalytic hydrogenation activity and selectivity of the hydrodewaxing catalyst are required to be improved in the actual preparation process of the transformer oil base oil, and the pressure drop of the catalyst bed layer is increased in the actual use process, which is not favorable for the long-term operation of the device. Meanwhile, the molecular sieve content in the hydrodewaxing is high, which results in higher cost of the catalyst.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of transformer oil base oil, which adopts a hydrodewaxing catalyst with a specific structure, low cost and high activity in a hydrodewaxing reaction process and combines a hydrofinishing process, so that the prepared transformer oil base oil product has high yield, low pour point and low aromatic hydrocarbon content. Meanwhile, the energy consumption of the device is reduced, and the running period of the device is long.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of transformer oil base oil comprises the following steps: and (3) sequentially carrying out hydrodewaxing reaction and hydrofinishing reaction on the raw oil to obtain the transformer oil base oil.
Optionally, the hydrodewaxing catalyst used in the hydrodewaxing reaction is:
comprises an active metal oxide and a catalyst carrier supporting the active metal oxide;
the catalyst carrier comprises a catalyst carrier support body with through holes on the surface and a molecular sieve membrane positioned on the surface of a pore channel of the support body, and the catalyst carrier support body with through holes on the surface comprises alumina and a metal oxide auxiliary agent, wherein the alumina and the metal oxide auxiliary agent form a spinel structure.
The hydrodewaxing catalyst adopts a unique carrier support preparation technology and prepares a special-shaped support, so that the final catalyst has high porosity and good permeability, is favorable for the diffusion of reactants and products, reduces the pressure drop of a dewaxing catalyst bed, and is favorable for the long-period operation of a device. Meanwhile, a ZSM-5 molecular sieve membrane is synthesized on the surface of the carrier support, so that the using amount of the molecular sieve in the catalyst is reduced, and the cost of the catalyst is reduced.
Optionally, the through holes are uniformly distributed on the catalyst support, preferably micro-and/or meso-holes, more preferably platinum-based micro-and meso-holes.
Optionally, the catalyst carrier support has a length of 1mm to 10mm, preferably 3mm to 8mm, an outer diameter of 4mm to 8mm, an inner hole diameter of 2mm to 4mm, and a surface through hole diameter of 1mm to 3mm.
Alternatively, the diameter of the through hole is 1mm to 3mm, and the shape of the through hole can be circular, rectangular, polygonal and the like, preferably circular.
Optionally, the catalyst carrier is in the form of particles, and the pore volume of the carrier is more than 0.750mL/g, and the specific surface area is more than 150m 2 /g。
Optionally, the molecular sieve has shape selective action and may be selected from ZSM-5.
Optionally, the hydrodewaxing catalyst comprises 1-21% of active metal oxide, 8-40% of molecular sieve and 1.0-5.4% of metal oxide additive by mass percent.
Optionally, the metal oxide auxiliary agent is one or two selected from NiO and CuO.
Optionally, the hydrodewaxing catalyst has a pore volume of 0.35-0.50 mL/g and a specific surface area of 230-260 m 2 /g。
Optionally, the active metal oxide is a group VIII and/or group VIB metal oxide, preferably NiO and WO 3 One or more of them.
Optionally, the hydrodewaxing catalyst comprises 1.0-6.0% of NiO and WO by mass percent 3 0 to 15 percent of the metal oxide, 8 to 40 percent of the molecular sieve and 1.0 to 5.4 percent of the metal oxide additive. Specifically, WO 3 The mass percentage of (B) includes but is not limited to 0, 0.5-15%, 0.5-10% and the like.
Optionally, the hydrodewaxing catalyst contains 1.0-6.0% of NiO by mass percent and WO 3 0.5-15%, molecular sieve 8-40%, metal oxide auxiliary agent 1.0-5.4%.
Optionally, the preparation of the hydrodewaxing catalyst comprises the following steps:
1) Preparing a molecular sieve mother solution, impregnating a catalyst carrier support body, crystallizing the impregnated material, washing, drying and roasting to obtain a catalyst carrier;
2) Preparing a salt solution of active metal, impregnating the catalyst carrier, drying and roasting to obtain the hydrodewaxing catalyst.
The pore-expanding agent with a certain particle size is added in the preparation process of the carrier support body, so that the prepared support body has a larger pore volume and a larger pore diameter, a large space is reserved for the synthesis of a subsequent molecular sieve, and a certain auxiliary agent is added in the preparation process, and the support body and alumina form a spinel structure after high-temperature roasting, so that the support body strength and the framework stability are improved, the acidity of the support body is reduced, and the product yield is improved.
Optionally, in step 1), the molecular sieve mother liquor is preferably a ZSM-5 mother liquor, and the specific components may be: in a molar ratio of Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 O = (0.025 to 0.25): (4-25): (0.03-0.3): (0.02 to 0.2): (10 to 150), wherein Al 2 O 3 Is provided by one or more of aluminum sulfate, aluminum nitrate and aluminum chloride, preferably aluminum sulfate; siO 2 2 Is provided by one of silica sol and ethyl orthosilicate, na 2 O is provided by sodium hydroxide; the template agent is one or more of triethylamine, tetraethylammonium hydroxide, diethylamine, dipropylamine and tripropylamine, and triethylamine is preferred; the crystallization is preferably carried out in a gas phase reaction kettle, more preferably, the impregnated material is placed at the upper part of the gas phase reaction kettle, deionized water is added at the bottom of the gas phase reaction kettle, and the reaction is carried out for 24 to 72 hours at the temperature of 160 to 230 ℃; optionally, the washing in step 1) is to wash the crystallized material to be neutral by using deionized water; optionally, in the step 1), the drying temperature is 120-150 ℃ and the drying time is 6-10 hours; optionally, in the step 1), the roasting temperature is 500-650 ℃ and the roasting time is 2-6 hours.
Optionally, in the step 1), the catalyst carrier containing the molecular sieve membrane can be obtained by repeating the steps of dipping, crystallizing, washing and drying according to the requirement of the catalyst on the content of the molecular sieve, and finally roasting.
Optionally, in the step 2), the salt solution of the active metal is a group VIII and/or VIB metal salt solution, preferably a nickel nitrate solution and/or a nickel nitrate-ammonium metatungstate solution, the NiO concentration of the solution is 0.0126 g/mL-0.095 g/mL, and WO 3 The concentration is 0-0.237 g/mL; the drying temperature is 120-150 ℃, and the drying time is 6-10 hours; the roasting temperature is 400-550 ℃ and the roasting time is 2-6 hours.
Optionally, the crystallization is performed in a gas phase reaction vessel. The steam in the gas phase reaction kettle is utilized for heating reaction, so that the synthesized molecular sieve is ensured to be totally gathered in the support body hole, and the waste of the molecular sieve is avoided
Optionally, the preparation of the catalyst support body comprises the steps of:
a. mixing and extruding pseudo-boehmite, peptizing agent, extrusion assistant, pore-expanding agent, metal oxide assistant precursor and water, performing shallow drying, and then performing granulation, drying and roasting to obtain the catalyst carrier support.
The addition of the pore-expanding agent ensures that the prepared support body has larger pore volume and pore diameter, and reserves larger space for the subsequent synthesis of the molecular sieve. The addition of the precursor of the metal oxide auxiliary agent forms a spinel structure with alumina after high-temperature roasting, improves the strength and the framework stability of the support body, reduces the acidity of the support body, and is beneficial to improving the product yield.
Optionally, the pseudoboehmite is a pseudoboehmite produced by an aluminum sulfate method, a carbonization method, an aluminum chloride method and the like which are commonly used in the industry at present; the pore volume of the pseudo-boehmite is more than 0.95mL/g, and the specific surface area is 280-330 m 2 /g。
Optionally, the mass ratio of the pseudoboehmite to the metal oxide promoter precursor is 1: 0.02-0.06.
Optionally, the metal oxide promoter precursor is selected from one or more of nickel nitrate and copper nitrate.
Optionally, in step a, the drying temperature is 120-150 ℃ and the drying time is 6-10 hours; the roasting temperature is 800-1000 ℃ and the roasting time is 2-6 hours.
Optionally, in step a, the mass ratio of the pseudo-boehmite, the peptizing agent, the extrusion aid, the pore-expanding agent, the metal oxide aid precursor and the water is 1:0.01 to 0.06:0.01 to 0.04:0.1 to 0.3: 0.02-0.06: 1.0 to 1.5.
Optionally, the peptizing agent is selected from one or more of nitric acid, acetic acid and citric acid.
Optionally, the extrusion aid is one or more of sesbania powder and methyl cellulose.
Optionally, the particle size of the pore-expanding agent is larger than 30 μm, and the pore-expanding agent is selected from one or more of carbon black, graphite and starch.
Optionally, the drying at a shallow degree refers to drying the strip-shaped object under constant humidity and constant temperature conditions until the solid content is 55% -75%, and the humidity inside and outside is consistent.
Optionally, the extrusion bar is shaped into a bar with a hollow extrusion part, the outer surface of the bar is cylindrical, clover-shaped or clover-shaped, the preferred outer shape is cylindrical, wherein the outer diameter of the bar is 4 mm-8 mm, the inner hollow diameter is 2 mm-4 mm, and the hollow shape can be circular, rectangular, polygonal, etc., preferably circular.
Optionally, the granulation is to make the extruded structure into granules with a length of 1mm to 10mm, preferably 3mm to 8mm.
Unless otherwise specified, the specific surface area and the pore volume were measured by a low-temperature nitrogen adsorption method.
Optionally, the operating conditions of the hydrodewaxing reaction are as follows: the reaction pressure is 10.0-20.0 MPa, the reaction temperature is 270-410 ℃, the volume ratio of hydrogen to oil is 300-2000, and the volume airspeed is 0.2-3.0 h -1 。
Optionally, the operating conditions of the hydrodewaxing reaction are: the reaction pressure is 12.0-18.0 MPa, the reaction temperature is 280-380 ℃, the volume ratio of hydrogen to oil is 500-1200, and the volume airspeed is 0.3-2.0 h -1 。
Optionally, the hydrofinishing catalyst used in the hydrofinishing reaction is: to contain 5 to 15% of SiO 2 Of gamma-Al 2 O 3 As carrier, W of IB group metalAnd/or Mo and Co and/or Ni of VIII group metal as active components, and one or more elements of P, F, B, ti and Zr as auxiliary agents.
Alternatively, the operating conditions of the hydrofinishing reaction are: the reaction pressure is 10.0-20.0 MPa, the reaction temperature is 250-380 ℃, the volume ratio of hydrogen to oil is 200-2000, and the volume airspeed is 0.3-3.5 h -1 。
Alternatively, the operating conditions of the hydrofinishing reaction are: the reaction pressure is 12.0-18.0 MPa, the reaction temperature is 260-340 ℃, the volume ratio of hydrogen to oil is 500-1200, and the volume airspeed is 0.5-2.0 h -1 。
Optionally, the raw oil is transformer oil.
The invention has the following beneficial effects:
in the preparation method provided by the invention, the specific hydrodewaxing catalyst is used to participate in the hydrodewaxing reaction, and in the preparation process of the hydrodewaxing catalyst, a unique carrier support preparation technology and a ZSM-5 molecular sieve membrane synthesis technology on the surface of a support body are adopted, so that the utilization rate of the molecular sieve is improved while the production cost of the catalyst is greatly reduced, the energy consumption is low in the process of processing the transformer oil, and the pour point of the obtained product is low. Meanwhile, in the catalyst forming process, an auxiliary agent is introduced, so that the acidity of the catalyst is reduced, and the product yield can be improved. Because of the independent special-shaped support body structure, the catalyst bed layer of the reactor has high void ratio and good permeability, and is beneficial to the long-period operation of the device.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
Respectively weighing the pore volume 1.095mL/g and the specific surface area 328m of the aluminum sulfate 2 500g of pseudo-boehmite with dry base of 71 percent, 18.4g of nitric acid with concentration of 65 percent, 10g of sesbania powder, 71g of carbon black, 60g of nickel nitrate auxiliary agent and 754g of deionized water are added into a rolling machine for rolling and mixing, and the mixture is extruded into a product with external diameter6mm cylindrical strips with an internal hollow diameter of 2.5mm were dried under constant humidity and temperature conditions to a solid content of 65%.
Punching circular through holes with the diameter of 1.5mm and uniformly arranged on the surface of the cylindrical strip by using punching equipment, preparing particles with the length of 3-10 mm, drying at 130 ℃ for 8h, and roasting at 900 ℃ for 3h to obtain the carrier support body.
Respectively weighing 7.52g of aluminum sulfate, 320g of silica sol containing 30% of silica, 2.15g of sodium hydroxide, 1.81g of triethylamine and 80g of water to prepare ZSM-5 molecular sieve mother liquor; and (2) soaking the carrier support body by using the prepared molecular sieve mother liquor, placing the soaked material on the upper part of a gas phase reaction kettle, adding deionized water into the bottom of the gas phase reaction kettle, reacting for 36 hours at 180 ℃, washing the product to be neutral by using the deionized water after the reaction is finished, drying the product for 8 hours at 130 ℃, and roasting the product for 3 hours at 550 ℃ to obtain the catalyst carrier containing the ZSM-5 molecular sieve membrane.
Weighing 30.3g of nickel nitrate to prepare a solution containing 0.019g/mL of nickel oxide, impregnating the catalyst carrier, drying the impregnated material at 120 ℃ for 8h, and roasting at 450 ℃ for 3h to obtain the hydrodewaxing catalyst A-1, wherein the properties of the catalyst are shown in Table 1.
Example 2
Respectively weighing the aluminum sulfate method produced pore volume of 1.095mL/g and the specific surface area of 328m 2 500g of pseudo-boehmite with a dry basis of 71 percent, 18.4g of nitric acid with a concentration of 65 percent, 10g of sesbania powder, 89g of starch, 43.7g of copper nitrate trihydrate assistant and 754g of deionized water are added into a rolling machine for rolling and mixing, extruded into a cylindrical strip with the outer diameter of 6mm and the hollow inside diameter of 2.5mm, and the strip is dried under the conditions of constant humidity and constant temperature until the solid content is 65 percent.
Punching circular through holes with the diameter of 1.5mm and uniformly arranged on the surface of the cylindrical strip by using punching equipment, preparing particles with the length of 3-10 mm, drying at 130 ℃ for 8h, and roasting at 900 ℃ for 3h to obtain the carrier support body.
Respectively weighing 15.53g of aluminum sulfate, 663g of silica sol containing 30 percent of silica, 4.45g of sodium hydroxide, 3.75g of triethylamine and 165.6g of water to prepare ZSM-5 molecular sieve mother liquor; and (2) impregnating the carrier support body by using one half of the prepared molecular sieve mother liquor, placing the impregnated material on the upper part of a gas phase reaction kettle, adding deionized water at the bottom of the gas phase reaction kettle, reacting for 36 hours at 180 ℃, washing the impregnated material to be neutral by using the deionized water after the reaction is finished, drying the impregnated material for 8 hours at 130 ℃, impregnating the dried material by using the residual molecular sieve mother liquor, placing the impregnated material on the upper part of the gas phase reaction kettle, adding the deionized water at the bottom of the gas phase reaction kettle, reacting for 36 hours at 180 ℃, washing the impregnated material to be neutral by using the deionized water after the reaction is finished, drying the impregnated material for 8 hours at 130 ℃, and roasting the impregnated material for 3 hours at 550 ℃ to obtain the catalyst carrier containing the ZSM-5 molecular sieve membrane.
Respectively weighing 50.4g of nickel nitrate and 83.3g of ammonium metatungstate to prepare a mixed solution containing 0.043g/mL of nickel oxide and 0.128g/mL of tungsten trioxide, impregnating the catalyst carrier, drying the impregnated material at 120 ℃ for 8 hours, and roasting at 450 ℃ for 3 hours to obtain the hydrodewaxing catalyst A-2, wherein the properties of the catalyst are shown in Table 1.
Comparative example 1
The preparation process of the Chinese patent CN1352231A as a comparative example is as follows: (1) Weighing the small-pore alumina (pore volume is 0.49mL/g, specific surface area is 229 m) 3 40.5g of water, adding 69.4g of purified water and 8.1mL of concentrated nitric acid, and uniformly mixing to prepare an adhesive; (2) Respectively weighing 126.3g of HZSM-5 molecular sieve, 3.0g of sesbania powder and the adhesive, kneading, extruding and forming; (3) Drying the wet strips at 100 +/-10 ℃ for 4h, and roasting at 730 ℃ for 4h to prepare a carrier; (4) 24.9g of nickel nitrate is dissolved by purified water to prepare 200ml of solution; (5) 100g of the carrier is put into the impregnation liquid, impregnated for 2h, then filtered, dried for 4h at 100 ℃, and calcined for 3h at 480 ℃ to prepare the catalyst B-1, the properties of the catalyst are shown in Table 1, and the evaluation results of the catalyst are shown in Table 3.
TABLE 1 Properties of catalysts of the invention and comparative examples
Example 3
A200 mL reactor device is adopted to carry out pilot test, diesel oil fraction of a hydro-upgrading device of a certain plant is taken as raw material (the properties of the raw material are shown in a table 2), and the raw material is required to be added>The pour point of the fraction with the temperature of 280 ℃ is reduced to be below minus 50 ℃ and the fraction is used for producing the transformer oil with the pour point of less than minus 50 ℃. The heterotype supporting body containing spinel structure, shape-selective cracking molecular sieve membrane hydrodewaxing catalyst and catalyst containing a certain SiO are sequentially filled according to the flowing direction of reaction material 2 The alumina is used as a supplementary refined catalyst of a carrier.
Wherein, the hydrodewaxing catalyst of the hydrodewaxing reactor is the catalyst prepared in the example 1 and the example 2.
The supplementary refining catalyst in the hydrogenation supplementary refining reaction zone is SiO-containing 2 9wt% of gamma-Al 2 O 3 As carrier, W-Mo-Ni as active component, P as assistant and WO as catalyst 3 Content 22wt%, moO 3 The content was 9wt%, the NiO content was 5wt%, and the P content was 1.2wt%.
The operating conditions of the hydrodewaxing reaction zone are as follows: the reaction pressure is 15MPa, the reaction temperature is 290 ℃, the volume ratio of hydrogen to oil is 800, and the volume space velocity is 1.0h -1 。
The operation conditions of the hydrofinishing reaction zone are as follows: the reaction pressure is 15MPa, the reaction temperature is 280 ℃, the volume ratio of hydrogen to oil is 800, and the volume airspeed is 0.5h -1 。
The properties of the feed oil are shown in Table 2, and the reaction conditions and the evaluation results are shown in Table 3.
TABLE 2 Properties of the feed oils
TABLE 3 evaluation of catalyst Process conditions and product Properties
As can be seen from Table 3, the fraction of more than or equal to 280 ℃ (transformer oil) is subjected to hydrodewaxing-hydrofinishing, the pour point can be reduced to-58 ℃ from-3 ℃ at a lower reaction temperature, the aromatic hydrocarbon content is reduced to below 0.5% from 14.7%, the yield is high, the fraction is a blending component of the base oil of the transformer oil with excessive quality, and the blending component can be blended with other transformer components to produce more transformer oil.
Example 4
In order to examine the stability of the hydrodewaxing catalyst of the present invention, and to enable long-term operation, 2500h stability test was conducted using the same raw oil as in example 3, and for comparison, a stability test was also conducted using a comparative example.
The hydrodewaxing catalyst of the invention adopts a unique carrier support preparation technology and prepares a special-shaped support, so that the final catalyst has high void ratio and good permeability, is beneficial to the diffusion of reactants and products, reduces the pressure drop of a dewaxing catalyst bed and is beneficial to the long-period operation of the device. In order to verify the stability of the catalyst and facilitate the long-term operation of the device, the stability of the catalyst is verified on a medium-sized hydrogenation test device similar to the process flow of an industrial device.
The main factor restricting the long-term operation of industrial equipment is the rapid increase of the pressure drop of the equipment, and the increase rate of the pressure drop is directly related to the void ratio of the catalyst and the bed permeability, namely the material flow distribution.
The hydrodewaxing catalyst of the invention adopts a unique carrier support body preparation technology and prepares a special-shaped support body, the finally formed catalyst entity adopts common filling, and the measured void ratio of the catalyst bed layer is 48.5 percent, which is higher than that of the commonly used cylindrical bar (42.0 percent) and cloverleaf-shaped (46.0 percent) catalysts.
In order to verify the stability of the long-term operation of the catalyst of the present invention, the catalyst was packed in a reactor similar to an industrial plant by a general packing method, and the raw oil of example 3 was examined for experimental comparison.
After the inventive hydrodewaxing catalyst and the reference hydrodewaxing catalyst are respectively loaded into a hydrogenation reactor, the measured static pressure drop at the inlet a and the outlet b of the hydrogenation reactor R1 is 0.010MPa and 0.012MPa respectively, and the initial dynamic pressure drop under the same condition is 0.024MPa and 0.040MPa respectively, therefore, the porosity of the inventive catalyst is higher than that of the reference catalyst, and the dynamic pressure drop is reduced by more than one third compared with that of the reference catalyst.
In addition, the radial temperature distribution in the catalyst bed of the hydrogenation reactor R1 was tested in the initial and final stages of the experimental investigation. When the radial temperature difference of the catalyst is tested, the temperature values t1, t2 and t3 at the upper part of the bed layer are the same, and the temperature values t4, t5 and t6 at the lower part of the bed layer are also the same; when the radial temperature difference of the reference catalyst is tested, the temperature values of t1, t2 and t3 at the upper part of the bed layer are the same, and the temperature values of t4, t5 and t6 at the lower part of the bed layer are 0.4 ℃, which shows that the material flow distribution of the catalyst is better than that of the reference catalyst.
The higher porosity and better distribution of material flow create basic conditions for the performance of the catalyst and the long-term stable operation of the device.
The results of the catalyst performance examination are shown in tables 4 to 5 below.
TABLE 4 EXAMPLE 4 Properties of test base stock
Table 5 example 4 catalyst evaluation process conditions and product properties
As can be seen from the test comparison result of the example 4, the hydrodewaxing catalyst disclosed by the invention has the characteristics of high porosity and good material flow distribution, and compared with a reference catalyst, the hydrodewaxing catalyst has the advantages of lower reaction temperature and better activity stability. Therefore, the catalyst of the present invention is more favorable for long-term stable operation of industrial plants.
It should be understood that the above-described embodiments of the present invention are examples for clearly illustrating the invention, and are not to be construed as limiting the embodiments of the present invention, and it will be obvious to those skilled in the art that various changes and modifications can be made on the basis of the above description, and it is not intended to exhaust all embodiments, and obvious changes and modifications can be made on the basis of the technical solutions of the present invention.
Claims (11)
1. The preparation method of the transformer oil base oil is characterized by comprising the following steps of: sequentially carrying out hydrodewaxing reaction and hydrofinishing reaction on raw oil to obtain the transformer oil base oil;
in the hydrodewaxing catalyst used in the hydrodewaxing reaction:
comprises an active metal oxide and a catalyst carrier supporting the active metal oxide;
the catalyst carrier comprises a catalyst carrier support body with through holes on the surface and a molecular sieve membrane positioned on the surface of a pore channel of the support body, and the catalyst carrier support body with through holes on the surface comprises alumina and a metal oxide auxiliary agent, wherein the alumina and the metal oxide auxiliary agent form a spinel structure;
the metal oxide auxiliary agent is one or two of NiO and CuO;
the pore volume of the catalyst carrier support is more than 0.750mL/g, and the specific surface area is more than 150m 2 /g；
The hydrodewaxing catalyst has the pore volume of 0.35-0.50 mL/g and the specific surface area of 230-260 m 2 /g；
The hydrodewaxing catalyst comprises, by mass, 1-21% of active metal oxide, 8-40% of molecular sieve and 1.0-5.4% of metal oxide additive.
2. The method of claim 1, wherein the hydrodewaxing catalyst is prepared by the steps of:
1) Preparing a molecular sieve mother solution, impregnating a catalyst carrier support body, crystallizing the impregnated material, washing, drying and roasting to obtain a catalyst carrier;
2) Preparing a salt solution of active metal, impregnating the catalyst carrier, drying and roasting to obtain the hydrodewaxing catalyst.
3. The production method according to claim 2, characterized in that the production of the catalyst carrier support body comprises the steps of:
a. mixing, extruding and molding pseudo-boehmite, peptizing agent, extrusion aid, pore-expanding agent, metal oxide aid precursor and water, and then granulating, drying and roasting to obtain the catalyst carrier support;
the mass ratio of the pseudo-boehmite to the metal oxide auxiliary agent precursor is 1:0.02 to 0.06 percent;
the metal oxide auxiliary agent precursor is selected from one or more of nickel nitrate and copper nitrate;
in the step a, the drying temperature is 120-150 ℃ and the drying time is 6-10 hours; the roasting temperature is 800-1000 ℃ and the roasting time is 2-6 hours.
4. The preparation method according to claim 3, wherein in the step a, the mass ratio of the pseudo-boehmite, the peptizing agent, the extrusion aid, the pore-expanding agent, the metal oxide aid precursor and the water is 1:0.01 to 0.06:0.01 to 0.04:0.1 to 0.3: 0.02-0.06: 1.0 to 1.5; the pore volume of the pseudo-boehmite is more than 0.95mL/g, and the specific surface area is 280-330 m 2 (ii)/g; the peptizing agent is selected from one or more of nitric acid, acetic acid and citric acid; the extrusion aid is one or more of sesbania powder and methyl cellulose; the particle size of the pore-expanding agent is larger than 30 mu m, and the pore-expanding agent is selected from one or more of carbon black, graphite and starch.
5. The preparation method according to claim 1, wherein the hydrodewaxing reaction is carried out under the following operating conditions: reaction pressure 100 to 20.0MPa, the reaction temperature is 270 to 410 ℃, the volume ratio of hydrogen to oil is 300 to 2000, and the volume space velocity is 0.2 to 3.0h -1 。
6. The preparation method of claim 5, wherein the reaction pressure is 12.0-18.0 MPa, the reaction temperature is 280-380 ℃, the volume ratio of hydrogen to oil is 500-1200, and the volume space velocity is 0.3-2.0 h -1 。
7. The preparation method according to claim 1, wherein the hydrofinishing catalyst used in the hydrofinishing reaction is: to contain 5 to 15% of SiO 2 Of gamma-Al 2 O 3 The carrier is W and/or Mo of IB group metal and Co and/or Ni of VIII group metal as active components, and one or more elements of P, F, B, ti and Zr as auxiliary agents.
8. The production method according to claim 7, wherein the hydrofinishing catalyst comprises, in terms of oxides: 15 to 35 weight percent of VIB group element, 4.0 to 10.0 weight percent of VIII group element and 1.0 to 10 weight percent of auxiliary agent.
9. The production method according to any one of claims 1 or 7, wherein the operating conditions of the hydrofinishing reaction are: the reaction pressure is 10.0-20.0 MPa, the reaction temperature is 250-380 ℃, the volume ratio of hydrogen to oil is 200-2000, and the volume airspeed is 0.3-3.5 h -1 。
10. The preparation method of claim 9, wherein the reaction pressure is 12.0-18.0 MPa, the reaction temperature is 260-340 ℃, the volume ratio of hydrogen to oil is 500-1200, and the volume space velocity is 0.5-2.0 h -1 。
11. The production method according to claim 1, wherein the raw material oil is a transformer oil.
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