CN116440887A - Modified alumina and production method thereof - Google Patents
Modified alumina and production method thereof Download PDFInfo
- Publication number
- CN116440887A CN116440887A CN202210008460.3A CN202210008460A CN116440887A CN 116440887 A CN116440887 A CN 116440887A CN 202210008460 A CN202210008460 A CN 202210008460A CN 116440887 A CN116440887 A CN 116440887A
- Authority
- CN
- China
- Prior art keywords
- modifier
- modified alumina
- reaction kettle
- reaction
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000003607 modifier Substances 0.000 claims abstract description 111
- 239000002245 particle Substances 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 239000012798 spherical particle Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 177
- 239000000243 solution Substances 0.000 claims description 129
- 239000007788 liquid Substances 0.000 claims description 106
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 81
- 229910052731 fluorine Inorganic materials 0.000 claims description 81
- 239000011737 fluorine Substances 0.000 claims description 81
- 150000004645 aluminates Chemical class 0.000 claims description 73
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 56
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 54
- 229910052796 boron Inorganic materials 0.000 claims description 54
- 230000032683 aging Effects 0.000 claims description 46
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 42
- 239000003960 organic solvent Substances 0.000 claims description 39
- 238000006386 neutralization reaction Methods 0.000 claims description 36
- 229910052698 phosphorus Inorganic materials 0.000 claims description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 32
- 239000011574 phosphorus Substances 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 28
- 235000013024 sodium fluoride Nutrition 0.000 claims description 28
- 239000011775 sodium fluoride Substances 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 26
- 239000003570 air Substances 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 25
- 239000012298 atmosphere Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000002378 acidificating effect Effects 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 125000005619 boric acid group Chemical group 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 125000005624 silicic acid group Chemical group 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 235000006481 Colocasia esculenta Nutrition 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical group [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 claims description 2
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 claims description 2
- PWNUFMCSLMQPHA-UHFFFAOYSA-N [B].[P].[F] Chemical compound [B].[P].[F] PWNUFMCSLMQPHA-UHFFFAOYSA-N 0.000 claims description 2
- VMXIWXRDAGKMMH-UHFFFAOYSA-N [B].[Si].[P].[F] Chemical compound [B].[Si].[P].[F] VMXIWXRDAGKMMH-UHFFFAOYSA-N 0.000 claims description 2
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 240000004270 Colocasia esculenta var. antiquorum Species 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000012876 carrier material Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 47
- 229910052708 sodium Inorganic materials 0.000 description 47
- 239000011734 sodium Substances 0.000 description 47
- 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 38
- 230000001105 regulatory effect Effects 0.000 description 33
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 29
- 239000005711 Benzoic acid Substances 0.000 description 14
- 235000010233 benzoic acid Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000008213 purified water Substances 0.000 description 12
- 239000012429 reaction media Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000003223 protective agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- -1 alkali metal aluminate Chemical class 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 244000205754 Colocasia esculenta Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- 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
- B01J35/651—50-500 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
-
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses modified alumina and a production method thereof. The modified alumina provided by the invention is spherical particles, and the concentration of the modifier in the inner region of the modified alumina particles is higher than that of the modifier in the outer region of the modified alumina particles; the thickness ratio of the inner area to the outer area of the modified alumina particles along the radial direction is 1:2-2:1. The modified alumina has the characteristics of large particle size, concentrated distribution, high specific surface area, large pore volume, high crystallinity, gradient reduction distribution of the modifier from inside to outside in the modified alumina particles and the like, and can be used as a carrier material of a poor-quality raw material hydrogenation catalyst.
Description
Technical Field
The invention relates to the field of alumina preparation, in particular to a method for continuously producing modified alumina.
Background
At present, the production mode of pseudo-boehmite mainly comprises an inorganic aluminum salt method and an organic aluminum salt method, and batch kettle reactors are adopted in the production process. Pseudo-boehmite is mainly prepared by a precipitation mechanism, wherein precipitation refers to a process of generating insoluble substances through chemical reaction in a liquid phase and forming a new solid phase to be settled out of the liquid phase. From classical theoretical analysis of precipitation, the precipitate formation process is divided into: (1) nucleation: because of the continuous collision motion of molecules or ions, the molecules in the local area are clustered, the aggregation is not only due to the collision among moving particles in the solution, but also the mutual adhesion of the moving particles through weak acting force (Van der Waals force), chemical bonds are generated through crystals, and the aggregation is solidified; (2) Crystal nucleus growth: cluster molecular particles are contacted with each other and combined to grow; wherein, the colloid is uniform, the particles are tiny, and the method has very strong effect on nucleation and crystal growth.
The coprecipitation method is a typical method for preparing aluminum hydroxide. The method is to prepare aluminum salt from raw materials by taking water as a medium, and then to control certain solution concentration, solution flow rate, temperature and reaction time, and to prepare the aluminum hydroxide by acid/alkali neutralization. However, the initial nuclei Al (OH) in the coprecipitation process 3 The polymer has complex structure, small molecular polarity and extremely small solubility, so that the aggregation rate is far higher than the orientation rate, and amorphous gelatinous precipitation is easy to generate, so that the polymer has low crystallinity, incomplete crystal form and unsatisfactory pore structure.
CN104549528B discloses a method for preparing ebullated bed catalyst. The method comprises the following steps: (1) Adding reaction liquid into the bottom of the impinging stream reactor, heating, and starting a bottom stirring paddle; (2) Combining an aqueous alkali metal aluminate solution with CO 2 The air flows are respectively injected from accelerating pipes at the upper part of the impinging stream reactor, and the alkali metal aluminate aqueous solution is atomized and then mixed with CO 2 The gas flow carries out gas-liquid impinging stream reaction to generate aluminum hydroxide crystal nucleus which enters intoA settling zone; (3) After the gas-liquid impact flow is finished, continuously adding an acidic aluminum salt aqueous solution and an alkali metal aluminum salt aqueous solution or an alkaline precipitant at the same time at the feed inlets II and III, regulating the pH value, and carrying out neutralization reaction; (4) Aging, filtering, washing and drying to obtain alumina dry gel; (5) Mixing alumina dry gel, small hole SB powder and sesbania powder uniformly, adding adhesive, forming a plastic body, extruding, forming, drying and roasting to obtain an alumina carrier, impregnating active metal, drying and roasting to obtain the fluidized bed catalyst. In the preparation method, the auxiliary agent is introduced into the catalyst together with the active metal in the step (5), and the auxiliary agent is in a uniform distribution state.
In the prior art, although the grain size is controlled by different methods so as to prepare pseudo-boehmite with different pore structures and properties, how to prepare macroporous alumina with high specific surface area, and the modifier in the alumina particles is in gradient decreasing distribution is also an important subject in the field of continuous research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides modified alumina and a production method thereof, in particular to a method for continuously producing macroporous modified alumina. The modified alumina has the characteristics of large particle size, concentrated distribution, high specific surface area, large pore volume, gradient decreasing distribution of the modifier from inside to outside in the alumina particles, and the like, and can be used as a carrier material of a poor-quality raw material hydrogenation catalyst.
The first aspect of the present invention provides a modified alumina, wherein the modified alumina is in the form of spherical particles, and the concentration of the modifier in the inner region of the modified alumina particles is at least 0.5 percentage point, preferably 0.5 to 2.5 percentage points, higher than the concentration of the modifier in the outer region of the modified alumina particles; the thickness ratio of the inner area to the outer area of the modified alumina particles along the radial direction is 1:2-2:1.
In the modified alumina, the modifier is at least one selected from fluorine, boron, phosphorus and silicon; preferably, the modifier is at least two selected from fluorine, boron, phosphorus and silicon, wherein the content of any one modifier accounts for 10-60% of the total mass of the modifier, and further preferably, the modifier is selected from fluorine-boron, silicon-phosphorus, boron-phosphorus, fluorine-boron-phosphorus or fluorine-boron-phosphorus-silicon.
In the modified alumina, the concentration of the modifier in the inner region of the modified alumina particles is 2.5-3.5 wt%; the concentration of the modifier is 0.8 to 2.0 weight percent in the outer region of the modified alumina particles.
The properties of the modified alumina of the invention are as follows: the pore volume is 0.8-1.0 mL/g; specific surface area of 280-320 m 2 The pore size of the polymer/g may be not less than 90nm, preferably 110 to 160nm, more preferably 130 to 160nm.
The particle size distribution of the modified alumina of the invention is as follows: the proportion of the particles with the particle size smaller than 100 mu m is 5% -10.0%, the proportion of the particles with the particle size of 100-200 mu m is 5.0% -10.0%, and the proportion of the particles with the particle size larger than 200 mu m is 85.0% -90.0%.
The relative crystallinity of the modified alumina of the present invention is not less than 90%, preferably 95% to 99%.
The second aspect of the present invention provides a method for producing the above modified alumina, comprising:
(1) Adding an acidic aluminate solution I containing a modifier, an alkaline aluminate solution I containing a modifier, an organic solvent and a polar metal seed crystal into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II;
(3) The sol II and the acidic aluminate solution II containing the modifier or the alkaline aluminate solution II containing the modifier flow in parallel and enter a second reaction kettle to be neutralized and gel to obtain a generated liquid III;
(4) The generated liquid III enters an aging kettle for aging;
(5) Drying and roasting the ageing material obtained in the step (4) to obtain the modified alumina;
wherein the mass of the modifier introduced into the modified alumina from step (3) is lower than the mass of the modifier introduced into the modified alumina from step (1).
The production method of the modified alumina is preferably carried out in a continuous mode, wherein a plurality of settling tanks used in the step (2) and a plurality of ageing tanks used in the step (4) can be arranged, and the continuous production is switched.
In the method of the present invention, when continuously producing the modified alumina, preferably, the first reaction vessel in the step (1) is operated in such a manner that the produced liquid I is discharged from the first reaction vessel by overflow. When the first reaction kettle is started, preferably, an organic solvent and a polar metal seed crystal are firstly added as base solution, and then an acidic aluminate solution I containing a modifier and an alkaline aluminate solution I containing a modifier are added in parallel flow for neutralization and gel formation until the generated solution I starts to be discharged out of the first reaction kettle. Wherein the addition amount of the organic solvent in the base solution is 1/5-1/2 of the actual effective use volume of the first reaction kettle; when the generated liquid I starts to be discharged from the first reaction kettle, the acid aluminate solution I containing the modifier and the alkaline aluminate solution I containing the modifier in the first reaction kettle are prepared by using Al 2 O 3 The addition amount of the polar metal salt seed crystal is 0.1-5.0%, preferably 0.5-4.0% based on the total mass of the simple substance.
In the method of the invention, when continuously producing the modified alumina, preferably, the second reaction kettle in the step (3) adopts an overflow type operation mode for discharging the generated liquid III out of the second reaction kettle. When the second reaction kettle is started, preferably, the bottom water is added first, and the acidic aluminate solution II containing the modifier or the alkaline aluminate solution II containing the modifier is added in parallel flow for neutralization and gel formation until the generated liquid III starts to be discharged from the second reaction kettle. Wherein, the addition amount of the bottom water is 1/7-1/2, preferably 1/6-1/3 of the actual effective use volume of the second reaction kettle.
In the method of the present invention, the organic solvent in the step (1) is an organic substance that is not or slightly soluble in water, and the organic substance may be one or more of alkane, alkene, organic alcohol, organic acid, etc., preferably, the carbon number of the organic substance is 5-12. Wherein the molecular structural formula of alkane is C n H 2n+2 (n is more than or equal to 5, preferably n=5-12), and at least one of pentane, hexane, dodecane and the like can be selected; molecular knots of olefinsThe structure is C n H 2n (n is more than or equal to 5, preferably n=5-12), and at least one of pentene, hexene and the like can be selected; the organic alcohol is at least one selected from organic monohydric alcohol and organic polyalcohol, wherein the molecular structural formula of the organic monohydric alcohol is C n H 2n+2 O (n is more than or equal to 6, preferably n=6-12), and at least one of n-hexanol, n-heptanol and the like can be selected; wherein the molecular structural formula of the polyol is C n H 2n+2-x (OH) x (n is more than or equal to 6, preferably n=6-12, and x is more than or equal to 3), and at least one of polyhydric alcohols such as pentaerythritol, glycerol, trimethylolethane, xylitol, sorbitol and the like can be selected; the organic acid may be at least one of aliphatic or aromatic carboxylic acid, such as benzoic acid.
In the method of the invention, the polar metal seed crystal is selected from at least one of metal halogen compounds and metal sulfides, preferably one or more of AgCl, znS, cuS or HgS and the like.
In the method of the invention, the operation conditions of the first reaction kettle in the step (1) are as follows: the temperature is-15 to 15 ℃, preferably 0 to 15 ℃, and the pressure is 1 to 10MPa, preferably 4 to 10MPa. The pressure atmosphere can be one or more of air, nitrogen or inert gas. The reaction conditions for neutralizing and gelling in the step (1) are as follows: the pH value is 2 to 6, preferably 2 to 5, and the reaction time is 10 to 180 minutes, preferably 10 to 60 minutes (when continuous production is employed, the reaction time is the residence time of the acidic aluminate solution I containing the modifier and the basic aluminate solution I containing the modifier into the first reaction vessel). The neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 150 to 500rad/min.
In the process of the present invention, the acidic aluminate of step (1) may be selected from AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of them, preferably Al 2 (SO 4 ) 3 、AlCl 3 The acidic aluminate solution may be an aqueous solution. The concentration of the acid aluminate in the acid aluminate aqueous solution containing the modifier is Al 2 O 3 Is 10 to 100g/100ml. The alkaline aluminate is selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 . The alkaline aluminate solution may be an aqueous solution. The concentration of the alkaline aluminate in the alkaline aluminate aqueous solution containing the modifier is Al 2 O 3 Is 10-100 g/100ml.
In the method of the invention, the modifier in the step (1) is at least one of fluorine, boron, phosphorus and silicon, and in the acid aluminate solution containing the modifier, the concentration of the modifier is calculated as simple substance, and the modifier accounts for the acid aluminate and is calculated as Al 2 O 3 2.5 to 3.5 weight percent of the weight; in the alkaline aluminate solution containing the modifier, the concentration of the modifier is calculated as simple substance, and the alkaline aluminate is calculated as Al 2 O 3 2.5 to 3.5 weight percent of the weight percent. The modifier source may be selected according to the acid-base of the solution, for example, the fluorine source is ammonium fluoride or sodium fluoride, the boron source is boric acid, sodium borate or ammonium borate, the phosphorus source is phosphoric acid or sodium phosphate, and the silicon source is silicic acid or sodium silicate.
In the method of the present invention, the organic solvent and the polar metal seed crystal are added to the first reaction kettle in parallel, wherein the addition rate of the organic solvent is the ratio of the addition rate of the acid aluminate solution I containing the modifier and the alkaline aluminate solution I containing the modifier in terms of the volume of the two to be 0.1:1 to 10:1, preferably 0.2:1 to 5:1, and the addition rate of the polar metal seed crystal is the addition rate of the acid aluminate solution I containing the modifier and the alkaline aluminate solution I containing the modifier in terms of Al 2 O 3 The sum of the addition rates of the sum modifier and the sum modifier is 1 to 10 percent, preferably 1 to 5 percent, of the total mass of the single substances.
In the method of the invention, the particle size distribution of the sol II obtained in the step (2) is as follows: the proportion of the grains with the grain diameter smaller than 50nm is 0.5-5.0%, the proportion of the grains with the grain diameter of 50-100 nm is 2-5%, and the proportion of the grains with the grain diameter larger than 100nm is 90-95%. The relative crystallinity of the obtained sol II is less than or equal to 95%, preferably 95% to 98%.
In the method of the present invention, the operating conditions of the settling tank of step (2) are as follows: the temperature is-15 to 15 ℃, preferably 0 to 15 ℃, and the pressure is 1 to 10MPa, preferably 4 to 10MPa.
In the method, after the sedimentation in the step (2), the organic solvent on the upper layer can be recycled to the first reaction kettle for continuous use.
In the process of the present invention, the acidic aluminate of step (3) is selected from AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 At least one of the following, preferably Al 2 (SO 4 ) 3 、AlCl 3 And the like, and the acidic aluminate solution may be an aqueous solution. The concentration of the acid aluminate in the acid aluminate aqueous solution containing the modifier is Al 2 O 3 Is 10-100 g/100ml. The alkaline aluminate is selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 The alkaline aluminate solution may be an aqueous solution. The concentration of the alkaline aluminate in the alkaline aluminate aqueous solution containing the modifier is Al 2 O 3 Is 10-100 g/100ml.
In the method of the invention, the modifier in the step (3) is at least one of fluorine, boron, phosphorus and silicon, and in the acid aluminate solution containing the modifier, the concentration of the modifier is calculated as simple substance, and the modifier accounts for the acid aluminate and is calculated as Al 2 O 3 0.8 to 2.0 weight percent of the weight; in the alkaline aluminate solution containing the modifier, the concentration of the modifier is calculated as simple substance, and the alkaline aluminate is calculated as Al 2 O 3 0.8 to 2.0 weight percent of the weight percent. The modifier source may be selected according to the acid-base of the solution, for example, the fluorine source is ammonium fluoride or sodium fluoride, the boron source is boric acid, sodium borate or ammonium borate, the phosphorus source is phosphoric acid or sodium phosphate, and the silicon source is silicic acid or sodium silicate.
In the method of the invention, the operation conditions of the second reaction kettle in the step (3) are as follows: the temperature is 50-100 ℃, preferably 75-100 ℃, preferably, the reaction temperature of the second reaction kettle is at least 70 ℃ higher than the reaction temperature of the first reaction kettle; the pressure is 1 to 10MPa, preferably 1 to 4MPa, and more preferably 2.5 to 4MPa. Preferably, the operating pressure of the second reactor is at least 1.0MPa lower than the operating pressure of the first reactor. The reaction conditions for neutralizing and gelling in the step (3) are as follows: the pH value is 7 to 12, preferably 7.5 to 10.0, and the reaction time is 10 to 180 minutes, preferably 10 to 120 minutes (when continuous production is employed, the reaction time is the residence time of the sol II and the acidic aluminate solution II containing the modifier or the basic aluminate solution II containing the modifier into the second reaction kettle). The neutralization and gelling reaction is preferably carried out under stirring at a rate of 100 to 500rad/min, preferably 200 to 500rad/min.
In the method of the present invention, the aging reaction conditions of step (4): the temperature is 100-200 ℃, the pressure is 1-10 MPa, the aging time is 100-360 min, and the preferable time is 150-250 min; the aging is carried out under stirring conditions, preferably at a stirring speed of 500 to 800r/min.
In the method of the invention, the drying temperature in the step (5) is 100-450 ℃, preferably 150-400 ℃, and the drying time is 1-10 hours, and the drying mode can be flash drying, cyclone drying, oven drying, spray drying and the like. The roasting temperature is 300-800 ℃, preferably 350-550 ℃, and the roasting time is 2-5 hours, preferably 2-4 hours. The roasting atmosphere is one or more of air, nitrogen or steam.
In a third aspect the invention provides a modified alumina produced by the above process.
In a fourth aspect, the present invention provides the use of a modified alumina as described above in a hydrogenation catalyst support.
In the application of the invention, the hydrogenation catalyst can be a hydrogenation catalyst for treating inferior heavy oil, such as a protective agent and/or a hydrogenation refining agent in the hydrogenation of residual oil, wax oil, coal tar and coal liquefied oil, and is preferably a hydrogenation protective agent.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the method for producing the modified alumina, firstly, an organic solvent which is insoluble with water is used as a reaction medium, polar metal salt is used as a seed crystal, a modifier is added into acidic aluminate and alkaline aluminate, and neutralization reaction is carried out under higher pressure and lower reaction temperature, so that on one hand, sol-gel particles generated by neutralization are wrapped by hydrophilic hydroxyl on the surface, all sol-gel particles in the organic solvent which is insoluble with water can not adhere to each other, under the action of the polar seed crystal, the characteristics of small molecules and large polarity are utilized, and the characteristic of large orientation rate are utilized, so that crystal form precipitation or colloidal particles with crystal structures are easy to form, on the other hand, brownian motion of sol-gel molecules or ions is reduced under higher pressure and lower temperature, aggregation into clusters due to continuous collision of the particles is reduced, and under lower pH value, namely, the acidic condition, generated pseudo-boehmite is kept, so that crystal grains in sol II are suitable and complete, and then the sol-gel particles with complete crystal forms are formed under the conditions of high pressure, namely, the high pH value is concentrated, the three-dimensional crystal form particles are prevented from forming large crystal form, and the crystal form alumina particles are concentrated under the conditions, and the characteristics of large crystal form alumina particle size is concentrated, and the crystal alumina particle size is formed.
2. The modified alumina provided by the invention has the characteristics of large surface area, large pore volume, concentrated particle size distribution, gradient reduced distribution of the modifier from inside to outside, high crystallinity and the like, is particularly suitable for being used as a carrier of a hydrogenation catalyst, and is used as a protective agent and/or a hydrogenation refining agent, preferably a protective agent, for heavy and inferior raw materials such as residual oil, wax oil, coal liquefied oil, coal tar and the like.
3. In the modified alumina provided by the invention, the gradient reduction distribution of the concentration of the modifier from inside to outside systematically optimizes the activity distribution of the catalyst particles prepared by the modified alumina, so that the catalyst activity is more excellent, more metal impurities are deposited in the catalyst, and the long-period stable operation of the catalyst is ensured.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of modified alumina particles of example 1 of the invention.
Detailed Description
The method for producing the modified alumina of the present invention will be described in more detail by way of specific examples. The examples are merely illustrative of specific embodiments of the method of the invention and do not constitute a limitation on the scope of the invention.
In the invention, the specific surface area, pore volume and pore diameter are measured by adopting a low-temperature liquid nitrogen adsorption method; the particle size distribution was measured using a laser particle size distribution meter.
In the present invention, the crystallinity was measured by X-ray diffraction (XRD), wherein the crystallinity was 100% in SB powder (Condea, germany). XRD characterization was performed using a Japanese physics D/max2500 type X-ray diffractometer: cu K alpha rays, a graphite monochromator, a tube voltage of 40kV, a tube current of 80mA, a scanning range of 10-70 degrees, a step length of 0.01 degrees and a scanning frequency of 1 degree/min.
In the invention, the concentration of the modifier on the modified alumina particles is measured by adopting a field emission scanning electron microscope, and the type of an electron gun is as follows: cold field emission gun, accelerating voltage: 0.1 kW-30 kW, resolution: 1.0nm (secondary electrons), 3.0nm (backscattered electrons), magnification: 25 to 1000000. In the test process, 5-10 points are respectively taken in the inner area and the outer area, and then the average value is obtained to obtain the modifier concentration in the corresponding area.
In the present invention, the inner region and the outer region of the modified alumina particles are two regions formed in a thickness ratio in the radial direction with the center of the particles as an initial point, the region including the center is the inner region, and the other region is the outer region.
Example 1
2L of n-hexanol was added as a reaction medium to 10L of the first reaction vessel I, 1.6g of AgCl was added, the pressure of the first reaction vessel I was adjusted to 5MPa, the temperature was 10℃and the atmosphere was air, and the stirring rate was 200rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and the fluorine-containing aluminum sulfate solution (the concentration of aluminum sulfate is controlled by Al 2 O 3 20g/100mL, the fluorine source is ammonium fluoride, and fluorine accounts for Al in the aluminum sulfate solution 2 O 3 2.5 wt.% of the mass) and a sodium fluoride-containing meta-aluminate solution (sodium meta-aluminate concentration in Al 2 O 3 The fluorine source is sodium fluoride, and the fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source is 10g/100mL 2 O 3 3.0wt% of the mass is respectively 20mL/min and 15mL/min, the pH value of the reaction is 2.5, and after neutralization reaction is carried out for 15min, a lower overflow port control valve is opened to enableThe resultant liquid I flows into a settling tank II, n-hexanol and AgCl are added into a first reaction kettle I at the rates of 10ml/min and 0.1g/min respectively, after the resultant liquid volume in the settling tank II reaches 1/2 of the resultant liquid volume, the resultant liquid is switched to a settling tank III, an organic solvent in the settling tank II is separated from a sol II, the organic solvent can be recycled into the first reaction kettle I, and the properties of the sol II A are shown in table 1.
2.5L of purified water was added to the second reaction vessel IV, the pressure of the second reaction vessel was adjusted to 4MPa, the temperature was 100℃and the stirring rate was 300rad/min. Opening a sol II feed inlet and an alkali liquor feed inlet at the upper end of the second reaction kettle, and adding the sol II and the fluorine-containing sodium metaaluminate solution (the concentration of sodium metaaluminate is Al 2 O 3 The fluorine source is sodium fluoride, and fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source is 30g/100mL 2 O 3 The flow rates of 1.5wt percent of the mass are 15mL/min and 20mL/min respectively, the pH value of the reaction is regulated to 7.5, and after the neutralization reaction is carried out for 60min, the generated liquid III is discharged out of the second reaction kettle.
The resulting solution III was fed into an aging vessel, the pressure of the aging vessel was adjusted to 10MPa, the temperature was 100 ℃, the stirring rate was 500rad/min, and after aging for 150min, the resulting solution was dried at 150℃for 4 hours by filtration, and calcined at 400℃for 3 hours under an air atmosphere to give a modified alumina A, the properties of which are shown in Table 2.
Example 2
2.5L of cyclohexane as a reaction medium was added to 10L of the first reaction vessel I, 9g of ZnS was added thereto, the pressure of the first reaction vessel I was adjusted to 7MPa, the temperature was 0℃and the atmosphere was air, and the stirring rate was 300rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and a phosphorus-containing aluminum sulfate solution (the concentration of aluminum sulfate is controlled by Al 2 O 3 The content is 30g/100ml, the phosphorus source is phosphoric acid, and the phosphorus accounts for Al in the aluminum sulfate solution 2 O 3 2.5 wt.% of the mass) and a sodium aluminosilicate containing solution (sodium metaaluminate concentration in Al 2 O 3 25g/100mL, the silicon source is sodium silicate, and the silicon accounts for Al in the sodium metaaluminate solution 2 O 3 The flow rates of 2.9wt percent of the mass are 30mL/min and 25mL/min respectively, the reaction pH value is 5.0, after neutralization reaction is carried out for 30min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II, and meanwhile, the generated liquid I flows into a first reaction kettleCyclohexane and ZnS are added into the reactor I at the rates of 15ml/min and 0.2g/min respectively, the reactor is switched to a settling tank III after the volume of the generated liquid in the settling tank II reaches 3/4 of the volume of the generated liquid, the organic solvent in the settling tank II is separated from the sol II, the organic solvent can be recycled to the first reaction kettle I, and the properties of the sol II B are shown in the table 1. The modifier phosphorus to silicon=50wt% to 50wt% in sol II B.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 3MPa, the temperature is 80 ℃, and the stirring speed is 300rad/min. Opening a sol II feed inlet and an acid liquid feed inlet at the upper end of the second reaction kettle, and controlling the sol II and the aluminum sulfate solution containing phosphorus and silicon (the concentration of aluminum sulfate is calculated as Al 2 O 3 25g/100mL, phosphoric acid as phosphorus source, silicic acid as silicon source, and Al in aluminum sulfate 2 O 3 The flow rates of 1.0wt percent of the mass are 20mL/min and 30mL/min respectively, the reaction pH value is 9.5, and after the neutralization reaction is carried out for 120min, the generated liquid III is discharged out of the second reaction kettle. The modifier phosphorus in the resultant liquid III was 50wt% to 50wt% of silicon.
The resultant solution III is put into an aging kettle, the pressure of the aging kettle is regulated to 10MPa, the temperature is 200 ℃, the stirring speed is 500rad/min, the aging is carried out for 180min, the mixture is filtered and dried for 5h at 180 ℃, and the mixture is baked for 4h at 350 ℃ in an air atmosphere, so that modified alumina B is obtained, and the properties of the modified alumina B are shown in Table 2.
Example 3
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and a boron-containing aluminum sulfate solution (the concentration of aluminum sulfate is controlled by Al 2 O 3 The content of boron is 40g/100mL, the boron source is boric acid, and the boron accounts for Al in the aluminum sulfate solution 2 O 3 2.7 wt.% of the mass) and a sodium fluoride-containing meta-aluminate solution (sodium meta-aluminate concentration in Al 2 O 3 The fluorine source is sodium fluoride, and the fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source accounts for 35g/100mL 2 O 3 The flow rates of 2.9wt percent of the mass are 20mL/min and 10mL/min respectively, the pH value of the reaction is 4.5, and after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated liquid to be generatedAnd I flows into a settling tank II, simultaneously, benzoic acid and CuS are added into a first reaction kettle I at the rates of 20ml/min and 0.5g/min respectively, after the volume of the generated liquid in the settling tank II reaches 2/3 of that of the generated liquid, the generated liquid is switched into the settling tank III, the organic solvent in the settling tank II is separated from the sol II, the organic solvent can be recycled into the first reaction kettle I, and the properties of the sol II C are shown in the table 1. Modifier fluorine: boron=45 wt% to 55wt% in sol II C.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 3.5MPa, the temperature is 90 ℃, and the stirring speed is 450rad/min. Opening a sol II feed inlet and an alkali liquor feed inlet at the upper end of the second reaction kettle, and controlling the sol II and the fluorine-containing sodium metaaluminate solution (the concentration of sodium metaaluminate is Al 2 O 3 The fluorine source is sodium fluoride, and fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source is 30g/100mL 2 O 3 The flow rates of 0.9wt percent of the mass are 10mL/min and 25mL/min respectively, the pH value of the reaction is adjusted to 9.5, and after the neutralization reaction is carried out for 100min, the generated liquid III is discharged out of the second reaction kettle.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 10MPa, the temperature to 150 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3h at 200 ℃ by filtering, and roasting for 4h at 500 ℃ in an air atmosphere to obtain modified alumina C, wherein the properties are shown in Table 2.
Example 4
4L of styrene is added into 10L of the first reaction kettle I as a reaction medium, 7g of HgS is added to regulate the pressure of the first reaction kettle I to 9MPa, the reaction temperature is 5 ℃, the atmosphere is air, and the stirring speed is 500rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and an aluminum sulfate solution containing boron and phosphorus is controlled (the concentration of aluminum sulfate is Al 2 O 3 50g/100mL, boric acid as boron source, phosphoric acid as phosphorus source, and Al in aluminum sulfate 2 O 3 2.7 wt.% of the mass) and sodium metaaluminate solution containing fluorine+silicon (sodium metaaluminate concentration as Al 2 O 3 25g/100mL, sodium fluoride as fluorine source, sodium silicate as silicon source, fluorine and silicon accounting for Al in sodium metaaluminate 2 O 3 3.0wt% of mass at a flow rate of 20mL/min and 15mL/min, respectively, at a pH of 4.5, and a neutralization reaction of 45m After in, a lower overflow port control valve is opened to enable the generated liquid I to flow into the high-pressure sedimentation tank II, meanwhile, styrene and HgS are respectively added into the high-pressure reaction tank I at the rates of 30ml/min and 0.5g/min, after the generated liquid volume in the high-pressure sedimentation tank II reaches 4/5 of the generated liquid volume, the generated liquid is switched into the high-pressure sedimentation tank III, the organic solvent in the high-pressure sedimentation tank II is separated from the sol II, the organic solvent can be recycled into the first reaction tank I, and the properties of the sol II D are shown in the table 1. In the sol II D, the modifier boron, fluorine, silicon and phosphorus are respectively 20wt percent, 30wt percent and 25wt percent.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 4.0MPa, the temperature is 85 ℃, and the stirring speed is 450rad/min. Opening a sol II feed inlet and an alkali liquor feed inlet at the upper end of the second reaction kettle, and controlling the sol II and an aluminum sulfate solution containing fluorine, silicon, boron and phosphorus (the concentration of aluminum sulfate is Al 2 O 3 45g/100mL, sodium fluoride as fluorine source, sodium silicate as silicon source, ammonium borate as boron source, sodium phosphate as phosphorus source, fluorine, silicon, boron and phosphorus accounting for Al in sodium metaaluminate 2 O 3 The flow rates of 1.4wt percent of the mass are 25mL/min and 40mL/min respectively, the pH value of the reaction is regulated to 7.5, and after the neutralization reaction is carried out for 80min, the generated liquid III is discharged out of the second reaction kettle. The modifier boron, fluorine, silicon and phosphorus in the generated liquid III are respectively 20 weight percent, 30 weight percent, 25 weight percent and 25 weight percent.
The resulting solution III was fed into an aging vessel, the pressure of the aging vessel was adjusted to 8.5MPa, the temperature was 180℃and the stirring rate was 500rad/min, and after aging for 210min, the resulting solution was dried by filtration at 180℃for 2 hours, and calcined at 400℃for 3 hours under an air atmosphere to give a modified alumina D, the properties of which are shown in Table 2.
Example 5
4L of styrene is added into 10L of the first reaction kettle I as a reaction medium, 7g of HgS is added to regulate the pressure of the first reaction kettle I to 9MPa, the reaction temperature is 5 ℃, the atmosphere is air, and the stirring speed is 500rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and an aluminum sulfate solution containing boron and phosphorus is controlled (the concentration of aluminum sulfate is Al 2 O 3 50g/100mL, boric acid as boron source, phosphoric acid as phosphorus source, and Al in aluminum sulfate 2 O 3 2.9wt% of mass) and fluorine-containing vinylideneSodium aluminate solution (sodium metaaluminate concentration with Al) 2 O 3 25g/100mL, the fluorine source is sodium fluoride, and fluorine accounts for Al in sodium metaaluminate 2 O 3 3.0wt% of mass is 20mL/min and 15mL/min respectively, the pH value of the reaction is 3.5, after the neutralization reaction is carried out for 45min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a high-pressure sedimentation tank II, meanwhile, styrene and HgS are added into the high-pressure reaction tank I at the rates of 30mL/min and 0.5g/min respectively, after the generated liquid volume in the high-pressure sedimentation tank II reaches 4/5 of the generated liquid volume, the generated liquid is switched into a high-pressure sedimentation tank III, the organic solvent in the high-pressure sedimentation tank II is separated from the sol II, the organic solvent can be recycled into the first reaction tank I, and the properties of the sol II E are shown in Table 1. In the sol II E, the modifier boron, fluorine and phosphorus are respectively 30 weight percent, 30 weight percent and 40 weight percent.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 2.8MPa, the temperature is 90 ℃, and the stirring speed is 450rad/min. Opening a sol II feed inlet and an alkali liquor feed inlet at the upper end of the second reaction kettle, and controlling the sol II and aluminum sulfate solution containing fluorine, boron and phosphorus (the concentration of aluminum sulfate is Al 2 O 3 45g/100mL, sodium fluoride as fluorine source, ammonium borate as boron source, sodium phosphate as phosphorus source, and Al in sodium metaaluminate 2 O 3 The flow rates of 1.4wt percent of the mass are 25mL/min and 40mL/min respectively, the pH value of the reaction is regulated to 7.5, and after the neutralization reaction is carried out for 80min, the generated liquid III is discharged out of the second reaction kettle. The modifier boron, fluorine and phosphorus in the generated liquid III are respectively 30 weight percent, 30 weight percent and 40 weight percent.
The resulting solution III was fed into an aging vessel, the pressure of the aging vessel was adjusted to 10MPa, the temperature was 200℃and the stirring rate was 500rad/min, and after aging for 210min, the resulting solution was dried at 180℃for 2 hours by filtration, and calcined at 400℃for 3 hours under an air atmosphere to give a modified alumina E, the properties of which are shown in Table 2.
Comparative example 1
5L of benzoic acid is added as a reaction medium to 10L of the first reaction kettle I, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to be normal, the temperature is 75 ℃, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and a boron-containing aluminum sulfate solution (the concentration of aluminum sulfate is controlled by Al 2 O 3 The content of boron is 40g/100mL, the boron source is boric acid, and the boron accounts for Al in the aluminum sulfate solution 2 O 3 2.7 wt.% of the mass) and a sodium fluoride-containing meta-aluminate solution (sodium meta-aluminate concentration in Al 2 O 3 The fluorine source is sodium fluoride, and the fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source accounts for 35g/100mL 2 O 3 2.9wt% of mass is 20mL/min and 10mL/min respectively, the pH value of the reaction is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II, meanwhile, benzoic acid and CuS are added into a first reaction kettle I at the rates of 20mL/min and 0.5g/min respectively, after the generated liquid volume in the settling tank II reaches 2/3 of the generated liquid volume, the generated liquid is switched into a settling tank III, the organic solvent in the settling tank II is separated from sol II, the organic solvent can be recycled into the first reaction kettle I, and the properties of sol II F are shown in table 1. Modifier fluorine: boron=45 wt% to 55wt% in sol IIF.
3L of purified water was added to the second reaction vessel IV, the pressure of the second reaction vessel was adjusted to normal pressure, the temperature was 75℃and the stirring rate was 450rad/min. Opening a sol II feed inlet and an alkali liquor feed inlet at the upper end of the second reaction kettle, and controlling the sol II and the fluorine-containing sodium metaaluminate solution (the concentration of sodium metaaluminate is Al 2 O 3 The fluorine source accounting for 30g/100mL is sodium fluoride, and fluorine accounts for Al in sodium metaaluminate solution 2 O 3 The flow rates of 0.9wt percent of the mass are 10mL/min and 25mL/min respectively, the pH value of the reaction is adjusted to 9.5, and after the neutralization reaction is carried out for 100min, the generated liquid III is discharged out of the second reaction kettle.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to be normal pressure, regulating the temperature to 75 ℃, stirring the mixture at the speed of 400rad/min, aging the mixture for 240min, drying the mixture at 200 ℃ for 3h through filtration, and roasting the mixture at 500 ℃ for 4h in an air atmosphere to obtain modified alumina F, wherein the properties are shown in Table 2.
Comparative example 2
5L of purified water is added into 10L of the first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and a boron-containing aluminum sulfate solution (the concentration of aluminum sulfate is controlled by Al 2 O 3 The content of boron is 40g/100mL, the boron source is boric acid, and the boron accounts for Al in the aluminum sulfate solution 2 O 3 2.7 wt.% of the mass) and a sodium fluoride-containing meta-aluminate solution (sodium meta-aluminate concentration in Al 2 O 3 The fluorine source is sodium fluoride, and the fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source accounts for 35g/100mL 2 O 3 2.9wt% of mass is 20mL/min and 10mL/min respectively, the pH value of the reaction is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II, meanwhile, benzoic acid and CuS are added into a first reaction kettle I at the rates of 20mL/min and 0.5G/min respectively, after the generated liquid volume in the settling tank II reaches 2/3 of the generated liquid volume, the generated liquid is switched into a settling tank III, the organic solvent in the settling tank II is separated from sol II, the organic solvent can be recycled into the first reaction kettle I, and the properties of sol II G are shown in table 1. Modifier fluorine: boron=45 wt% to 55wt% in sol II G.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 3.5MPa, the temperature is 90 ℃, and the stirring speed is 450rad/min. Opening a sol II feed inlet and an alkali liquor feed inlet at the upper end of the second reaction kettle, and controlling the sol II and the fluorine-containing sodium metaaluminate solution (the concentration of sodium metaaluminate is Al 2 O 3 The fluorine source accounting for 30g/100mL is sodium fluoride, and fluorine accounts for Al in sodium metaaluminate solution 2 O 3 The flow rates of 0.9wt percent of the mass are 10mL/min and 25mL/min respectively, the pH value of the reaction is adjusted to 9.5, and after the neutralization reaction is carried out for 100min, the generated liquid III is discharged out of the second reaction kettle.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 10MPa, regulating the temperature to 150 ℃, stirring at the speed of 400rad/min, aging for 240min, drying at 200 ℃ for 3h by filtering, and roasting at 500 ℃ for 4h under an air atmosphere to obtain modified alumina G, wherein the properties are shown in Table 2.
Comparative example 3
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and a boron-containing aluminum sulfate solution (the concentration of aluminum sulfate is controlled by Al 2 O 3 The content of boron is 40g/100mL, the boron source is boric acid, and the boron accounts for Al in the aluminum sulfate solution 2 O 3 2.7 wt.% of the mass) and a sodium fluoride-containing meta-aluminate solution (sodium meta-aluminate concentration in Al 2 O 3 The fluorine source is sodium fluoride, and the fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source accounts for 35g/100mL 2 O 3 The flow rates of 2.9wt percent of the mass are 20mL/min and 10mL/min respectively, the reaction pH value is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II, meanwhile, benzoic acid is added into a first reaction tank I at the rate of 20mL/min, after the generated liquid volume in the settling tank II reaches 2/3, the generated liquid is switched to a settling tank III, an organic solvent in the settling tank II is separated from a sol II, the organic solvent can be recycled into the first reaction tank I, and the properties of the sol II H are shown in table 1. Modifier fluorine: boron=45 wt% to 55wt% in sol II H.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 3.5MPa, the temperature is 90 ℃, and the stirring speed is 450rad/min. Opening a sol II feed inlet and an alkali liquor feed inlet at the upper end of the second reaction kettle, and controlling the sol II and the fluorine-containing sodium metaaluminate solution (the concentration of sodium metaaluminate is Al 2 O 3 The fluorine source accounting for 30g/100mL is sodium fluoride, and fluorine accounts for Al in sodium metaaluminate solution 2 O 3 The flow rates of 0.9wt percent of the mass are 10mL/min and 25mL/min respectively, the pH value of the reaction is adjusted to 9.5, and after the neutralization reaction is carried out for 100min, the generated liquid III is discharged out of the second reaction kettle.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 10MPa, regulating the temperature to 150 ℃, stirring at the speed of 400rad/min, aging for 240min, drying at 200 ℃ for 3H by filtering, and roasting at 500 ℃ for 4H under an air atmosphere to obtain modified alumina H, wherein the properties are shown in Table 2.
Comparative example 4
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 200 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and a boron-containing aluminum sulfate solution (the concentration of aluminum sulfate is controlled by Al 2 O 3 The content of the boron source is 40g/100mL, and the boron source is boric acidBoron occupies Al in the aluminum sulfate solution 2 O 3 2.7 wt.% of the mass) and a sodium fluoride-containing meta-aluminate solution (sodium meta-aluminate concentration in Al 2 O 3 The fluorine source is sodium fluoride, and the fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source accounts for 35g/100mL 2 O 3 2.9wt% of mass is 20mL/min and 10mL/min respectively, the pH value of the reaction is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II, meanwhile, benzoic acid and CuS are added into a first reaction kettle I at the rates of 20mL/min and 0.5g/min respectively, after the generated liquid volume in the settling tank II reaches 2/3 of the generated liquid volume, the generated liquid is switched into a settling tank III, the organic solvent in the settling tank II is separated from sol II, the organic solvent can be recycled into the first reaction kettle I, and the properties of the sol II are shown in table 1. Modifier fluorine: boron=45 wt% to 55wt% in sol II I.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 3.5MPa, the temperature is 90 ℃, and the stirring speed is 450rad/min. Opening a sol II feed inlet and an alkali liquor feed inlet at the upper end of the second reaction kettle, and controlling the sol II and the fluorine-containing sodium metaaluminate solution (the concentration of sodium metaaluminate is Al 2 O 3 The fluorine source accounting for 30g/100mL is sodium fluoride, and fluorine accounts for Al in sodium metaaluminate solution 2 O 3 The flow rates of 0.9wt percent of the mass are 10mL/min and 25mL/min respectively, the pH value of the reaction is adjusted to 9.5, and after the neutralization reaction is carried out for 100min, the generated liquid III is discharged out of the second reaction kettle.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 10MPa, regulating the temperature to 150 ℃, stirring at the speed of 400rad/min, aging for 240min, drying at 200 ℃ for 3h by filtering, and roasting at 500 ℃ for 4h under an air atmosphere to obtain alumina I, wherein the properties are shown in Table 2.
Comparative example 5
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After the mixture is uniformly stirred, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 40g/100mL and a sodium metaaluminate solution with the concentration of 35g/100mL are controlled to be 20mL/min and 10mL/min respectively, the reaction pH value is 4.5, after the neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable a generated liquid I to flow into a settling tank II, simultaneously benzoic acid and CuS are added into the first reaction kettle I at the flow rates of 20mL/min and 0.5g/min respectively, after the generated liquid volume in the settling tank II reaches 2/3, the generated liquid is switched to a settling tank III, an organic solvent in the settling tank II is separated from the sol II, the organic solvent can be recycled into the first reaction kettle I, and the properties of the sol II J are shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 3.5MPa, the temperature is 90 ℃, and the stirring speed is 450rad/min. And opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, controlling the flow rates of the sol II and the sodium metaaluminate solution with the concentration of 30g/100mL to be 10mL/min and 25mL/min respectively, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after neutralization reaction for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 10MPa, regulating the temperature to 150 ℃, stirring at the speed of 400rad/min, aging for 240min, drying at 200 ℃ for 3h by filtering, and roasting at 500 ℃ for 4h under an air atmosphere to obtain modified alumina J, wherein the properties are shown in Table 2.
Comparative example 6
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and a boron-containing aluminum sulfate solution (the concentration of aluminum sulfate is controlled by Al 2 O 3 The content of boron is 40g/100mL, the boron source is boric acid, and the boron accounts for Al in the aluminum sulfate solution 2 O 3 1.5 wt.% of the mass) and a sodium fluoroaluminate solution (sodium metaaluminate concentration in Al 2 O 3 The fluorine source is sodium fluoride, and the fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source accounts for 35g/100mL 2 O 3 1.5wt% of the mass is respectively 20mL/min and 10mL/min, the pH value of the reaction is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II, and simultaneously benzoic acid and CuS are respectively added into a first reaction kettle I at the rates of 20mL/min and 0.5g/min untilAfter the volume of the generated liquid in the settling tank II reaches 2/3 of that of the generated liquid, the generated liquid is switched to the settling tank III, the organic solvent in the settling tank II is separated from the sol II, the organic solvent can be recycled to the first reaction kettle I, and the properties of the sol II K are shown in the table 1. Modifier fluorine: boron=45 wt% to 55wt% in sol II K.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 3.5MPa, the temperature is 90 ℃, and the stirring speed is 450rad/min. Opening a sol II feed inlet and an alkali liquor feed inlet at the upper end of the second reaction kettle, and controlling the sol II and the fluorine-containing sodium metaaluminate solution (the concentration of sodium metaaluminate is Al 2 O 3 The fluorine source is sodium fluoride, and fluorine accounts for Al in the sodium metaaluminate solution, wherein the fluorine source is 30g/100mL 2 O 3 The flow rates of the mixed solution with the mass of 1.5wt percent are respectively 10mL/min and 25mL/min, the pH value of the reaction is adjusted to 9.5, and after the neutralization reaction is carried out for 20min, the generated liquid III is discharged out of the second reaction kettle.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 10MPa, the temperature to 150 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3h at 200 ℃ by filtering, and roasting for 4h at 500 ℃ in an air atmosphere to obtain modified alumina K, wherein the properties are shown in Table 2.
TABLE 1 Properties of Sol II obtained in examples and comparative examples (to follow)
| A | B | C | D | E | |
| Relative crystallinity,% | 98 | 96 | 99 | 98 | 96 |
| Particle size distribution, percent | |||||
| ＜50nm | 0.8 | 0.6 | 0.7 | 0.5 | 0.9 |
| 50～100nm | 5.0 | 4.8 | 4.2 | 4.5 | 4.9 |
| ＞100nm | 94.2 | 94.6 | 95.1 | 95.0 | 94.2 |
TABLE 1 Properties of the sols II obtained in examples and comparative examples (follow-up)
| F | G | H | I | J | K | |
| Relative crystallinity,% | 85 | 90 | 82 | 93 | 95 | 96 |
| Particle size distribution, percent | ||||||
| ＜50nm | 11.7 | 15.9 | 8.9 | 9.9 | 0.9 | 0.8 |
| 50～100nm | 11.4 | 19.7 | 17.9 | 10.6 | 4.3 | 4.9 |
| ＞100nm | 76.9 | 64.4 | 71.4 | 79.5 | 94.8 | 94.3 |
TABLE 2 Properties (to be continued) of the alumina obtained in examples and comparative examples
Table 2 Properties of the alumina obtained in examples and comparative examples (follow-up)
Example 6
This example describes the preparation of original solutions of Mo, ni, P.
157g of molybdenum oxide and 69g of basic nickel carbonate are put into a multi-neck flask, a certain amount of deionized water is added, stirring is carried out until substances in the flask are in a slurry state, then 53g of phosphoric acid is slowly added, after the initial reaction, the solution is slowly heated again, the temperature of the solution is kept at 100 ℃ for 2 hours, after the heating is stopped, the obtained solution is filtered while the solution is hot, and a clear dark green initial solution is obtained. The solution composition is MoO 3 ：35.27g/100ml；NiO：8.32g/100ml；P：2.19g/100ml。
Example 7
The modified aluminas of examples 1, 2, 3, 4, and 5 were saturated with the solution of example 6, dried at 120℃for 3 hours, and calcined at 500℃for 3 hours to give the desired catalysts A, B, C, D and E, respectively. And then the catalysts are respectively subjected to activity comparison tests on a 100mL fixed bed small hydrogenation device, and the feeding mode adopts upper feeding. The properties of the raw oil are shown in Table 3; the evaluation conditions are shown in Table 4; the evaluation results of the catalyst are shown in Table 5.
Comparative example 7
The modified aluminas of comparative examples 1, 2, 3, 4, 5, and 6 were saturated with the solution of example 6, dried at 120℃for 3 hours, and calcined at 500℃for 3 hours to give the desired catalysts F, G, H, I, J and K, respectively. And then the catalysts are respectively subjected to activity comparison tests on a 100mL fixed bed small hydrogenation device, and the feeding mode adopts upper feeding. The properties of the raw oil are shown in Table 3; the evaluation conditions are shown in Table 4; the evaluation results of the catalyst are shown in Table 5.
TABLE 3 Properties of raw oil
Table 4 evaluation of process conditions
| Reaction temperature, DEG C | 410 |
| Partial pressure of reaction hydrogen, MPa | 15.9 |
| Liquid hourly space velocity, h -1 | 0.20 |
| Hydrogen to oil volume ratio | 1100 |
TABLE 5 evaluation results (waiting) of the catalysts obtained in examples and comparative examples
TABLE 5 evaluation results (waiting) of the catalysts obtained in examples and comparative examples
As can be seen from tables 1 and 2, the modified alumina provided by the invention has the advantages of large specific surface area, high pore volume, high crystallinity and concentrated grain distribution, and is very suitable for the hydrotreating protective agent carrier of heavy inferior raw materials.
Claims (24)
1. A modified alumina, which is spherical particles, the concentration of the modifier in the inner region of the modified alumina particles being at least 0.5 percent, preferably 0.5 to 2.5 percent, higher than the concentration of the modifier in the outer region of the modified alumina particles; the thickness ratio of the inner area to the outer area of the modified alumina particles along the radial direction is 1:2-2:1.
2. The modified alumina of claim 1, wherein the modifier is selected from at least one of fluorine, boron, phosphorus, and silicon; preferably, the modifier is at least two selected from fluorine, boron, phosphorus and silicon, wherein the content of any modifier accounts for 10-60% of the total mass of the modifier; further preferably, the modifier is selected from fluorine-boron, silicon-phosphorus, boron-phosphorus, fluorine-boron-phosphorus or fluorine-boron-phosphorus-silicon.
3. The modified alumina according to claim 1 or 2, wherein the concentration of modifier in the inner region of the modified alumina particles is 2.5 to 3.5wt%; the concentration of the modifier is 0.8 to 2.0 weight percent in the outer region of the modified alumina particles.
4. The modified alumina according to claim 1, wherein the modified alumina has a pore volume of 0.8 to 1.0mL/g and a specific surface area of 280 to 320m 2 The pore size of the polymer/g may be as low as 90nm, preferably 110 to 160nm.
5. The modified alumina of claim 1, wherein the modified alumina has a particle size distribution of: the proportion of the particles with the particle size smaller than 100 mu m is 5% -10.0%, the proportion of the particles with the particle size of 100-200 mu m is 5% -10.0%, and the proportion of the particles with the particle size larger than 200 mu m is 85.0% -90.0%.
6. The modified alumina of claim 1, wherein said modified alumina has a relative crystallinity of not less than 90%, preferably from 95% to 99%.
7. The method for producing a modified alumina according to any one of claims 1 to 6, comprising:
(1) Adding an acidic aluminate solution I containing a modifier, an alkaline aluminate solution I containing a modifier, an organic solvent and a polar metal seed crystal into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II;
(3) The sol II and an acidic aluminate solution II containing a modifier or an alkaline aluminate solution II containing a modifier flow in parallel and enter a second reaction kettle to be neutralized and gel to obtain a generated liquid III;
(4) The generated liquid III enters an aging kettle for aging;
(5) Drying and roasting the ageing material obtained in the step (4) to obtain the modified alumina;
wherein the mass of the modifier introduced into the modified alumina from step (3) is lower than the mass of the modifier introduced into the modified alumina from step (1).
8. The production method according to claim 7, wherein the production method is performed in a continuous manner.
9. The production method according to claim 8, wherein a plurality of settling tanks used in the step (2) and aging tanks used in the step (4) are provided for switching; the first reaction kettle in the step (1) adopts an overflow type operation mode for discharging the generated liquid I out of the first reaction kettle, and the second reaction kettle in the step (3) adopts an overflow type operation mode for discharging the generated liquid III out of the second reaction kettle.
10. The production method according to claim 8, wherein when the first reaction kettle is started, an organic solvent and a polar metal seed crystal are added as a base solution, and then an acidic aluminate solution I containing a modifier and an alkaline aluminate solution I containing a modifier are added in parallel flow for neutralization and gel formation until the generated solution I starts to discharge from the first reaction kettle; wherein the addition amount of the organic solvent in the base solution is 1/5-1/2 of the actual effective use volume of the first reaction kettle; when the generated liquid I starts to discharge the first reaction kettle, the acid aluminate solution I containing the modifier and the alkaline aluminate solution I containing the modifier in the first reaction kettle are prepared by using Al 2 O 3 And the addition amount of the polar metal salt seed crystal accounts for 0.1 to 5.0 percent, preferably 0.5 to 4.0 percent, based on the total mass of the modifier simple substance.
11. The production method according to claim 8, wherein when the second reaction kettle is started up, the bottom water is added first, then the sol II and the acid aluminate solution II containing the modifier or the alkaline aluminate solution II containing the modifier are added in parallel flow for neutralization and gel formation until the generated liquid III starts to be discharged out of the second reaction kettle; wherein, the addition amount of the bottom water is 1/7-1/2, preferably 1/6-1/3 of the actual effective use volume of the second reaction kettle.
12. The process according to any one of claims 7 to 11, wherein the organic solvent in step (1) is an organic substance which is not miscible or slightly soluble with water and is selected from one or more of alkanes, alkenes, organic alcohols, organic acids; preferably, the organic matter has a carbon number of 5 to 12.
13. The production method according to any one of claims 7 to 11, wherein the polar metal seed crystal is selected from one or more of AgCl, znS, cuS or HgS.
14. The process according to any one of claims 7 to 11, wherein the first reactor of step (1) is operated under the following conditions: the temperature is-15 to 15 ℃, preferably 0 to 15 ℃, the pressure is 1 to 10MPa, preferably 4 to 10MPa; the reaction conditions for neutralizing and gelling in the step (1) are as follows: the pH value is 2-6, preferably 2-5, the reaction time is 10-180 minutes, preferably 10-60 minutes; the neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 150 to 500rad/min.
15. The process according to any one of claims 7 to 11, wherein in step (1) or step (3), the acidic aluminate is selected from the group consisting of AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of them, preferably Al 2 (SO 4 ) 3 、AlCl 3 One or more of the above, wherein the concentration of the acid aluminate in the acid aluminate aqueous solution containing the modifier is Al 2 O 3 Counting to be 10-100 g/100ml; the alkaline aluminate is selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 The concentration of the alkali aluminate in the alkali aluminate aqueous solution containing the modifier is Al 2 O 3 Is 10-100 g/100ml.
16. The process according to any one of claims 7 to 11, wherein in step (1), the modifier is at least one of fluorine, boron, phosphorus and silicon, and the concentration of the modifier is calculated as elemental substance in the acidic aluminate solution containing the modifier, and the concentration of the modifier is calculated as Al in the acidic aluminate solution 2 O 3 2.5 to 3.5 weight percent of the weight; in the alkaline aluminate solution containing the modifier, the concentration of the modifier is calculated as simple substance, and the alkaline aluminate is calculated as Al 2 O 3 Meter mass2.5 to 3.5 weight percent of the total weight of the mixture; in the modifier source, the fluorine source is ammonium fluoride or sodium fluoride, the boron source is boric acid, sodium borate or ammonium borate, the phosphorus source is phosphoric acid or sodium phosphate, and the silicon source is silicic acid or sodium silicate.
17. The production method according to any one of claims 7 to 11, characterized in that the organic solvent and the polar metal seed crystal are added to the first reaction vessel in parallel, wherein the addition rate of the organic solvent is such that the ratio of the addition rate of the acidic aluminate solution i containing the modifier and the basic aluminate solution i containing the modifier in terms of both volumes is 0.1:1 to 10:1, preferably 0.2:1 to 5:1, the adding rate of the polar metal seed crystal is that the acid aluminate solution I containing the modifier and the alkaline aluminate solution I containing the modifier are added with Al 2 O 3 And 1 to 10 percent of the sum of the addition rates of the modifier elements by mass, preferably 1 to 5 percent.
18. The process according to any one of claims 7 to 11, wherein the sol ii obtained in step (2) has a particle size distribution as follows: the proportion of the grains with the grain diameter smaller than 50nm is 0.5-5.0%, the proportion of the grains with the grain diameter of 50-100 nm is 2-5%, and the proportion of the grains with the grain diameter larger than 100nm is 90-95%; preferably, the relative crystallinity of the obtained sol II is less than 95%, preferably 95% to 98%.
19. The production process according to any one of claims 7 to 11, characterized in that the operating conditions of the settling tank of step (2) are as follows: the temperature is-15 to 15 ℃, preferably 0 to 15 ℃, and the pressure is 1 to 10MPa, preferably 4 to 10MPa.
20. The process according to any one of claims 7 to 11, wherein in step (3), the modifier is at least one of fluorine, boron, phosphorus and silicon, and the modifier is contained in an acidic aluminate solution having a concentration of the modifier in terms of simple substance, based on Al in the acidic aluminate 2 O 3 0.8 to 2.0 weight percent of the weight; in alkaline aluminate solution containing modifierThe concentration of the sex agent is calculated by simple substance and the concentration of the sex agent accounts for the alkali aluminate to be Al 2 O 3 0.8 to 2.0 weight percent of the weight; in the modifier source, the fluorine source is ammonium fluoride or sodium fluoride, the boron source is boric acid, sodium borate or ammonium borate, the phosphorus source is phosphoric acid or sodium phosphate, and the silicon source is silicic acid or sodium silicate.
21. The process according to any one of claims 7 to 11, wherein the second reactor of step (3) is operated under the following conditions: the temperature is 50-100 ℃, preferably 75-100 ℃, the pressure is 1-10 MPa, preferably 1-4 MPa; the reaction conditions for neutralizing and gelling in the step (3) are as follows: the pH value is 7-12, preferably 7.5-10.0, the reaction time is 10-180 minutes, preferably 10-120 minutes; the neutralization and gelling reaction is preferably carried out under stirring at a rate of 100 to 500rad/min, preferably 200 to 500rad/min.
22. The production method according to any one of claims 7 to 11, wherein in step (4), the aging reaction conditions are: the temperature is 100-200 ℃, the pressure is 1-10 MPa, the aging time is 100-360 min, and the preferable time is 150-250 min; the aging is carried out under stirring conditions, preferably at a stirring speed of 500 to 800r/min.
23. The production method according to any one of claims 7 to 11, characterized in that in step (5), the drying temperature is 100 to 450 ℃, preferably 150 to 400 ℃, and the drying time is 1 to 10 hours; the roasting temperature is 300-800 ℃, preferably 350-550 ℃, the roasting time is 2-5 hours, preferably 2-4 hours, and the roasting atmosphere is one or more of air, nitrogen or water vapor.
24. Use of the modified alumina of any one of claims 1-6 in a hydrogenation catalyst support.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210008460.3A CN116440887B (en) | 2022-01-06 | 2022-01-06 | Modified alumina and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210008460.3A CN116440887B (en) | 2022-01-06 | 2022-01-06 | Modified alumina and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116440887A true CN116440887A (en) | 2023-07-18 |
| CN116440887B CN116440887B (en) | 2024-08-06 |
Family
ID=87134288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210008460.3A Active CN116440887B (en) | 2022-01-06 | 2022-01-06 | Modified alumina and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116440887B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527369A (en) * | 1994-11-17 | 1996-06-18 | Saint-Gobain/Norton Industrial Ceramics Corp. | Modified sol-gel alumina |
| US20070056879A1 (en) * | 2005-06-28 | 2007-03-15 | Patrick Euzen | Process for producing middle distillates by hydroisomerizing and hydrocracking feeds from the fischer-tropsch process using a doped catalyst based on mesoporous alumina-silica with a controlled macropore content |
| CN104117359A (en) * | 2013-04-27 | 2014-10-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN106669851A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Spherical alumina carrier and preparation method thereof |
-
2022
- 2022-01-06 CN CN202210008460.3A patent/CN116440887B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527369A (en) * | 1994-11-17 | 1996-06-18 | Saint-Gobain/Norton Industrial Ceramics Corp. | Modified sol-gel alumina |
| US20070056879A1 (en) * | 2005-06-28 | 2007-03-15 | Patrick Euzen | Process for producing middle distillates by hydroisomerizing and hydrocracking feeds from the fischer-tropsch process using a doped catalyst based on mesoporous alumina-silica with a controlled macropore content |
| CN104117359A (en) * | 2013-04-27 | 2014-10-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN106669851A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Spherical alumina carrier and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116440887B (en) | 2024-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4085068A (en) | Hydrodenitrogenation and hydrocracking catalyst | |
| CN109718796B (en) | Hydrogenation catalyst and preparation method thereof | |
| CN109718794B (en) | Fluidized bed hydrogenation catalyst and preparation method thereof | |
| CN116440887B (en) | Modified alumina and production method thereof | |
| CN116443905B (en) | Modified alumina and method for producing the same | |
| CN116440888B (en) | Macroporous modified alumina and production method thereof | |
| CN116440886B (en) | Macroporous modified alumina and its production process | |
| CN116440913B (en) | Modified hydrogenation catalyst and preparation method thereof | |
| CN116440915B (en) | Modified hydrogenation catalyst and preparation method thereof | |
| CN116081662B (en) | Alumina and production method thereof | |
| CN118164514A (en) | A modified aluminum oxide and a production method thereof | |
| CN116060023B (en) | Hydrogenation catalyst and preparation method thereof | |
| CN114057213A (en) | Preparation method of macroporous alumina material | |
| CN116440912B (en) | Macroporous modified hydrogenation catalyst and production method thereof | |
| CN116440914B (en) | Macropore modified hydrogenation catalyst and production method thereof | |
| CN116081664B (en) | Macroporous alumina and its production process | |
| CN114749170B (en) | Silicon-aluminum particle aggregate, and manufacturing method and application thereof | |
| CN112742408A (en) | Dry gas hydrogenation saturated olefin and desulfurization catalyst, and preparation method and application thereof | |
| CN116060022B (en) | Hydrogenation catalyst and production method thereof | |
| CN118164512A (en) | Modified alumina and production method thereof | |
| CN118145690A (en) | Modified alumina and preparation method thereof | |
| CN118162174A (en) | Hydrogenation catalyst and preparation method thereof | |
| CN118164513A (en) | A modified aluminum oxide and a preparation method thereof | |
| CN118162176A (en) | Hydrogenation catalyst and production method thereof | |
| CN114057211A (en) | Preparation method of aluminum oxide material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240202 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Country or region after: China Applicant after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100020 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant before: CHINA PETROLEUM & CHEMICAL Corp. Country or region before: China Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |