CN114425350B - Heavy oil hydrotreating catalyst and preparation method thereof - Google Patents
Heavy oil hydrotreating catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN114425350B CN114425350B CN202011182283.8A CN202011182283A CN114425350B CN 114425350 B CN114425350 B CN 114425350B CN 202011182283 A CN202011182283 A CN 202011182283A CN 114425350 B CN114425350 B CN 114425350B
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- China
- Prior art keywords
- catalyst
- impregnating solution
- carrier
- phosphorus
- boron
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 239000000295 fuel oil Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 239000011800 void material Substances 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims description 28
- 239000011574 phosphorus Substances 0.000 claims description 28
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000008187 granular material Substances 0.000 claims description 16
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 15
- -1 amine compound Chemical class 0.000 claims description 13
- 238000004898 kneading Methods 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 8
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 235000015165 citric acid Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 241000219782 Sesbania Species 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 6
- 239000001923 methylcellulose Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical compound OCNCO OTJFQRMIRKXXRS-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 235000011087 fumaric acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 2
- 229940087646 methanolamine Drugs 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 11
- 239000000084 colloidal system Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000009792 diffusion process Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000002245 particle Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 241000219793 Trifolium Species 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 229910000480 nickel oxide Inorganic materials 0.000 description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000000265 homogenisation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000008213 purified water Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229960004011 methenamine Drugs 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004939 coking Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001646834 Mesona Species 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a heavy oil hydrotreating catalyst and a preparation method thereof. The catalyst comprises a carrier and an active metal component; the void ratio of the catalyst in dense phase filling is more than 43.5%, preferably 45% -50%, and more preferably 46% -48%. The catalyst has larger pore volume and pore diameter, and has larger bed void ratio, so that the diffusion resistance of asphaltene and colloid macromolecules in the pore canal of the catalyst can be effectively reduced, and the hydroconversion efficiency is improved. Is especially suitable for the hydroconversion process of asphaltene and colloid macromolecules in the raw materials in the heavy oil hydrotreatment process.
Description
Technical Field
The invention relates to a heavy oil hydrotreating catalyst and a preparation method thereof, in particular to a residual oil hydrotreating catalyst for removing asphaltene and colloid macromolecules and a preparation method thereof.
Technical Field
Heavy oils, particularly residuum, contain significant amounts of sulfur, nitrogen, metal and other impurities as well as non-ideal components such as polycyclic aromatic hydrocarbons, gums, asphaltenes and the like. The main purpose of heavy oil hydrotreatment, especially residual oil hydrotreatment process, is to remove impurities therein through hydrotreatment, improve the quality of oil products, and provide guarantee for the next oil product treatment.
The fixed bed residuum hydrogenation technology is a common heavy oil deep processing technology, in which normal pressure or vacuum residuum is desulfurized, denitrified, demetallized, etc. under the condition of high temperature and high pressure in a fixed bed reactor filled with specific catalyst, so as to obtain light products to the maximum extent, and is one of the important means for lightening residuum. The fixed bed residual oil hydrogenation technology has the advantages of high liquid product yield, good product quality and the like, and is increasingly widely applied.
The fixed bed residuum hydrogenation technology, while having many advantages, is prone to increased reactor pressure drop during the production process. The heavy oil is mainly due to the fact that the heavy oil is high in viscosity, metal impurities or asphaltene are high, metal and coke can be gradually deposited on the catalyst in the hydrogenation process, the catalyst is easy to deactivate rapidly, a bed layer is blocked, and pressure is increased. Especially, asphaltene and colloid macromolecules in residual oil are enriched with a large amount of metals and easy-to-coke precursors, and the deactivation of the catalyst is directly influenced.
Therefore, how to effectively carry out hydroconversion on asphaltene and colloid macromolecules and slow down the rapid deactivation of a catalyst caused by coking, and is still an important research topic in the heavy oil hydrotreatment process.
Disclosure of Invention
The invention aims to provide a hydrotreating catalyst and a preparation method thereof, aiming at the problems of insufficient hydrogenation capability of heavy components in residual oil, particularly insufficient hydrogenation conversion capability of asphaltene and colloid macromolecules in the prior art. To increase its packing void fraction, reduce bed pressure drop during use, and further improve the properties of heavy oil hydroprocessing catalysts.
The first aspect of the invention is to provide a heavy oil hydroprocessing catalyst comprising a support and an active metal component; the void ratio of the catalyst in dense phase filling is more than 43.5%, preferably 45% -50%, and more preferably 46% -48%.
In the technical scheme, the catalyst is granular, the cross section of the catalyst is clover-shaped, and the diameter of the circumcircle of the catalyst is 1.3-4.0 mm, preferably 2.0-3.5 mm.
In the technical scheme, the specific surface area of the catalyst is 100-180 m 2 Preferably 130 to 180m 2 /g; the pore volume is 0.55-0.90 cm 3 Preferably 0.55 to 0.80 cm/g 3 Preferably 0.55 to 0.70 cm/g 3 And/g. The average pore diameter is 14nm to 35nm, preferably 15nm to 20nm.
In the above technical scheme, the carrier has the following properties: specific surface area of 150-250 m 2 Preferably 180 to 220m 2 And/g. The pore volume is 0.7-0.9 cm 3 Preferably 0.75 to 0.85 cm 3 And/g. The water absorption is 1.00-1.30, preferably 1.05-1.20.
In the technical scheme, the carrier is granular, the cross section of the carrier is clover-shaped, and the diameter of a circumcircle of the granule is 1.3-4.0 mm, preferably 2.0-3.5 mm.
In the technical scheme, the carrier preferably contains auxiliary agent phosphorus and/or boron, and the content of the auxiliary agent phosphorus and/or boron is 0.5% -5.0%, preferably 0.7% -3.0% by weight of the carrier. The support is preferably an alumina support.
In the above technical solution, the active metal includes at least one metal selected from group VIII and at least one metal selected from group VIB. The group VIII metal is preferably nickel and/or cobalt. The group VIB metal is preferably molybdenum and/or tungsten, most preferably molybdenum. The content of the VIB group metal in terms of oxide is 5% -15%, preferably 7.0% -13.0% by mass of the catalyst; the content of the VIII group metal is 1.0% -4.0% by oxide, preferably 1.5% -3.0%.
The second aspect of the present invention is to provide a method for producing a hydrotreating catalyst, comprising the steps of:
(1) Preparing a catalyst carrier: taking pseudo-boehmite, adding a pore-enlarging agent and an adhesive, kneading, forming, drying and roasting to obtain a catalyst carrier;
(2) Preparing an active metal impregnating solution containing an auxiliary agent: preparing an active metal impregnating solution, wherein the impregnating solution contains 10-90 g/L of phosphorus and/or boron, and the content of the active metal impregnating solution is preferably 20-70 g/L in terms of phosphorus and/or boron;
(3) Impregnating the carrier in the step (1) with the impregnating solution in the step (2), and drying and roasting to obtain the hydrotreating catalyst.
In the above technical solution, the pore-expanding agent in the step (1) is preferably one or more of carbon black, methylcellulose, sesbania powder, polyethylene glycol, starch and the like, and most preferably one or more of sesbania powder, methylcellulose and carbon black. The adhesive is a neutral adhesive, preferably hydroxypropyl methylcellulose. The kneading process may be either a milling process or a kneading process, preferably a milling process. The rolling time is 10 to 100 minutes, preferably 20 to 50 minutes. The forming is carried out so that the particles are formed into granular materials, the cross section of the particles is clover-shaped, and the diameter of the circumcircle of the particles is 1.3-4.0 mm, preferably 2.0-3.5 mm.
The drying in the step (1) is performed at 90-130 ℃ for 40-360 minutes, preferably at 100-120 ℃ for 60-240 minutes. The roasting is carried out at a temperature rising rate of 3.5-20 ℃/min, preferably 8-15 ℃/min, and a constant temperature of 700-900 ℃, preferably 720-850 ℃.
In the step (1), the pseudo-boehmite is preferably produced by adopting an aluminum sulfate method, and the auxiliary agent phosphorus and/or boron is added, wherein the content of the phosphorus and/or boron is 0.5% -5.0%, preferably 0.7% -3.0% by weight of the carrier. The pseudo-boehmite contains phosphorus and/or boron, and the prepared carrier has better thermal stability and surface chemical property, and is beneficial to the hydrogenation reaction of residual oil macromolecules.
In the above technical solution, the active metal in step (2) includes at least one metal selected from group VIII and at least one metal selected from group VIB. The group VIII metal is preferably nickel and/or cobalt. The group VIB metal is preferably molybdenum and/or tungsten, most preferably molybdenum. The active metal content in the impregnating solution is calculated by oxide, wherein the VIB group metal is molybdenum trioxide, and the content is 90-400 g/L, preferably 90-240 g/L, and more preferably 100-130 g/L; the group VIII metal is preferably nickel oxide and/or cobalt oxide, and the content is 15-150 g/L, preferably 18-60 g/L, more preferably 18-30 g/L. Preferably, an amine compound is added into the impregnating solution in the step (2); the amine compound is one or more of hexamethylenetetramine, ethylenediamine, octylamine, methanolamine, dimethanol amine, trimethanolamine, propanolamine, dipropanolamine, tripropanolamine, polyalcohol amine, ethanolamine, diethanolamine and triethanolamine; the content of the amine compound in the impregnating solution is 6 g/L-20 g/L, preferably 8 g/L-15 g/L. Preferably adding surfactant to the soaking solution in the step (2), wherein the surfactant is one or more of Tween-20, tween-30, tween-40, tween-60, tween-80 and Tween-85, preferably Tween-60 and/or Tween-80; the content of the surfactant in the impregnating solution is 2-80 g/L, preferably 5-50 g/L.
In the above technical solution, the impregnating solution in step (2) is preferably added with an organic acid compound, where the organic acid is one or more of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid and malic acid, and preferably citric acid. The content of the organic acid compound in the impregnating solution is 2-120 g/L, preferably 4-50 g/L.
The catalyst prepared by the invention is particularly suitable for the hydroconversion process of asphaltene and colloid macromolecules in raw materials in the heavy oil hydroprocessing process. The preparation method is simple in preparation process, environment-friendly and safe, and other operations do not need to be changed.
The catalyst prepared by the method has larger pore volume and pore diameter and larger bed void ratio, can effectively reduce the diffusion resistance of asphaltene and colloid macromolecules in the pore canal of the catalyst, and improves the hydroconversion efficiency. The higher bed void fraction can effectively relieve the rapid increase of pressure drop caused by coking among catalyst particles.
In the method, a mixture of an amine compound and a surfactant and active metal ions (nickel ions or cobalt ions) in the solution are preferably adopted to form a special compound, so that the structural composition of phosphomolybdate formed in the solution can be regulated, the adsorption heat generated in the process of contacting the solution with the surface of a carrier is reduced in the impregnation process, the interaction between the active metal and alumina is reduced, and the hydrogenation performance of the catalyst is improved.
The catalyst carrier for the hydrotreating process provided by the invention preferably adopts pseudo-boehmite containing phosphorus or boron auxiliary agent as a raw material, and the carrier preparation process adopts a non-acidic adhesive and a pore-expanding agent so as to further prepare the catalyst with larger pore volume and pore diameter.
Detailed Description
The following examples are given to illustrate the technical scheme of the present invention in further detail, but do not limit the scope of the present invention.
In the invention, pore volume, pore diameter and specific surface area are measured by using ASAP2420 type physical adsorption instrument of America microphone instruments. The sample is subjected to vacuum pretreatment for 4 hours at 300 ℃ and then isothermal N is carried out at 77K 2 Adsorption-desorption experiments.
In the invention, the void fraction of the catalyst is measured by a measuring cylinder method. The specific method comprises the following steps: (1) measuring the water absorption lambda of the catalyst. 50g of catalyst is accurately weighed, the catalyst is put into medium water, and no bubbles are generated on the surface of the catalyst after the catalyst is placed for 60 minutes. M accurately weighing the aqueous catalyst after wiping the water on the surface of the catalyst particles with a wet gauze 1 . Catalyst water absorption λ= (M) 1 -50)/50. (2) 1 measuring cylinder with volume of 2000mL is selected, and M is accurately weighed 2 . The catalyst is closely packed to a density d 1 g/mL. 1000mL of catalyst was weighed in close packing, catalyst weight M 3 =d 1 X 1000. Will M 3 g catalyst was wetted with water and saturated, after no bubbles had been generated on the catalyst surface, all were transferred to a 2000mL graduated cylinder and water was added to 1800mL. The total weight of the measuring cylinder, the catalyst, the water in the catalyst pore canal, the water among the catalyst gaps and 800mL of water is measured to be M 4 . Weight M of 1000mL of water between catalyst interstices 5 =M 4 -800-M 3 ×λ×1.0-M 3 -M 2 Then the volume of water between the catalyst voids is V 1 =M 5 /1.0. (3) Catalyst void ratio = V 1 /1000。
In the present invention, the void fraction of each catalyst was measured as described above. The medium water used in the method can also be ethanol, kerosene, gasoline, diesel oil and the like.
Example 1
700g of phosphorus-containing (1 wt%) pseudo-boehmite, 10g of hydroxypropyl methylcellulose, 50g of sesbania powder and 900g of deionized water are weighed. Mixing the materials, adding into a kneader, forming a plastic body through a kneading operation unit, and obtaining the granular material with clover shape through an extrusion molding method. The shaped particulate material was dried at 120℃for 260 minutes. The dried sample was placed in a muffle furnace. Roasting at the constant temperature of 800 ℃ at the heating rate of 3.5 ℃/min to obtain the carrier Z-1.
The cross-sectional shape of the obtained carrier Z-1 particles is clover-shaped, and the diameter of the circumcircle of the particles is 3.0mm. The carrier properties are as follows: specific surface area of 210m 2 Per g, pore volume of 0.84cm 3 And/g. The water absorption was 1.15.
11.8g of molybdenum trioxide (containing 99wt% of molybdenum oxide), 4.3g of basic nickel carbonate (containing 54wt% of nickel oxide) and 5.3g of phosphoric acid solution (containing 26.7wt% of phosphorus) are accurately weighed, purified water is added, the mixture is reacted for 30 minutes at normal temperature, 2.1g of citric acid is added, the mixture is reacted for 30 minutes continuously, and then heating, heating and boiling are started until the raw materials are completely dissolved. Keeping the temperature for 70 minutes, and then cooling to 25 ℃ for standby. Slowly adding 1.0g of a mixture of the trimethanolamine and 2.9g of tween-40 into the solution under the stirring state, stirring until the solution becomes clear, maintaining the stirring state for 30 minutes, stopping, and fixing the volume to 115mL for later use. 100g of Z-1 carrier is weighed, and the obtained impregnating solution is fully mixed with the carrier Z-1 by adopting a spraying method. The sample after the complete homogenization treatment is placed in a closed container at room temperature for 3.5 hours, then dried at 110 ℃ for 3 hours, and finally baked at 570 ℃ for 3.5 hours to prepare the catalyst ZC-1.
Example 2
700g of boron-containing (3 wt%) pseudo-boehmite, 10g of hydroxypropyl methylcellulose, 40g of carbon black and 880g of deionized water are weighed. Mixing the materials, adding into a kneader, forming a plastic body through a kneading operation unit, and obtaining the granular material with clover shape through an extrusion molding method. After the molding, the granular material was dried at 120℃for 240 minutes. And (3) placing the dried sample into a muffle furnace, and roasting at a constant temperature of 820 ℃ at a heating rate of 4.5 ℃/min to obtain the carrier Z-2.
The cross-sectional shape of the obtained carrier Z-2 particles is clover-shaped, and the diameter of the circumcircle of the particles is 2.6mm. The carrier properties are as follows: specific surface area of 170m 2 Per g, pore volume of 0.78cm 3 And/g. The water absorption was 1.10.
10.9g of molybdenum trioxide (containing 99wt percent of molybdenum oxide), 4.2g of basic nickel carbonate (containing 54wt percent of nickel oxide) and 8.3g of phosphoric acid solution (containing 26.7wt percent of phosphorus) are accurately weighed, put into a beaker according to a certain sequence, added with purified water, reacted for 30 minutes at normal temperature, added with 3.9g of salicylic acid, reacted for 30 minutes, and heated and boiled until the raw materials are completely dissolved. Keeping the temperature for 60 minutes, and then cooling to 25 ℃ for standby. Slowly adding 1.3g of hexamethylene tetramine and 3.0g of tween-60 mixture into the solution under stirring, stirring until the solution becomes clear, maintaining the stirring state for 40 minutes, stopping, and fixing the volume to 115mL for later use. 100g of Z-2 carrier is weighed, and the obtained impregnating solution is fully mixed with the carrier Z-2 by adopting a spraying method. The sample after the complete homogenization treatment is placed under a closed container at room temperature for 5.0 hours, then dried at 130 ℃ for 3 hours, and finally baked at 560 ℃ for 3.0 hours to prepare the catalyst ZC-2.
Example 3
700g of boron-containing (2 wt%) pseudo-boehmite, 10g of modified starch, 10g of polyethylene glycol, 20g of methylcellulose and 920g of deionized water are weighed. Mixing the materials, adding into a kneader, forming a plastic body through a kneading operation unit, and obtaining the granular material with clover shape through an extrusion molding method. After the molding, the granular material was dried at 120℃for 250 minutes. And (3) placing the dried sample into a muffle furnace, and roasting at a constant temperature of 800 ℃ at a heating rate of 5.5 ℃/min to obtain the carrier Z-3.
The cross-sectional shape of the obtained carrier Z-3 particles is clover-shaped, and the diameter of the circumcircle of the particles is 2.0mm. The carrier properties are as follows: specific surface area of 200m 2 Per g, pore volume of 0.80cm 3 And/g. The water absorption was 1.08.
14.7g of molybdenum trioxide (containing 99wt% of molybdenum oxide), 5.8g of basic nickel carbonate (containing 54wt% of nickel oxide) and 5.9g of phosphoric acid solution (containing 26.7wt% of phosphorus) are accurately weighed, put into a beaker according to a certain sequence, added with purified water, reacted for 40 minutes at normal temperature, added with 2.6g of tartaric acid, and continuously reacted for 30 minutes, and then heated and boiled until the raw materials are completely dissolved. Keeping the temperature for 70 minutes, and then cooling to 25 ℃ for standby. Slowly adding 1.6g of tripropanolamine and 3.6g of tween-30 mixture into the solution under stirring, stirring until the solution becomes clear, maintaining the stirring state for 40 minutes, stopping, and fixing the volume to 115mL for later use. 100g of Z-3 carrier is weighed, and the obtained impregnating solution is fully mixed with the carrier Z-3 by adopting a spraying method. The sample after the complete homogenization treatment is placed under a room temperature closed container for 5.0 hours, then dried for 3 hours at 125 ℃, and finally baked for 3.0 hours at 575 ℃ to prepare the catalyst ZC-3.
Example 4
700g of pseudo-boehmite containing phosphorus (1 wt%) and boron (1 wt%) were weighed out, 10g of hydroxypropyl methylcellulose, 10g of polyethylene glycol, 15g of methylcellulose and 910g of deionized water. Mixing the materials, adding into a kneader, forming a plastic body through a kneading operation unit, and obtaining the granular material with clover shape through an extrusion molding method. After the molding, the granular material was dried at 120℃for 250 minutes. And (3) placing the dried sample into a muffle furnace, and roasting at a constant temperature of 800 ℃ at a heating rate of 5.5 ℃/min to obtain the carrier Z-4.
The cross-sectional shape of the obtained carrier Z-4 particles is clover-shaped, and the diameter of the circumcircle of the particles is 2.5mm. The carrier properties are as follows: specific surface area of 190m 2 Per g, pore volume of 0.81cm 3 And/g. The water absorption was 1.16.
13.7g of molybdenum trioxide (containing 99wt percent of molybdenum oxide), 5.1g of basic nickel carbonate (containing 54wt percent of nickel oxide) and 5.2g of phosphoric acid solution (containing 26.7wt percent of phosphorus) are accurately weighed, put into a beaker according to a certain sequence, added with purified water, reacted for 40 minutes at normal temperature, added with 2.8g of tartaric acid, and continuously reacted for 35 minutes, and then heated and boiled until the raw materials are completely dissolved. Keeping the temperature for 70 minutes, and then cooling to 25 ℃ for standby. Slowly adding 1.2g of tripropanolamine and 4.3g of tween-30 mixture into the solution under stirring, stirring until the solution becomes clear, maintaining the stirring state for 40 minutes, stopping, and fixing the volume to 115mL for later use. 100g of Z-4 carrier is weighed, and the obtained impregnating solution is fully mixed with the carrier Z-4 by adopting a spraying method. The sample after the complete homogenization treatment is placed under a room temperature closed container for 5.0 hours, then dried for 3 hours at 125 ℃, and finally baked for 3.0 hours at 575 ℃ to prepare the catalyst ZC-4.
Example 5
700g of pseudo-boehmite containing phosphorus (1 wt%) is weighed, 10g of hydroxypropyl methylcellulose, 50g of sesbania powder and 900g of deionized water. Mixing the materials, adding into a kneader, forming a plastic body through a kneading operation unit, and obtaining the granular material with clover shape through an extrusion molding method. The shaped particulate material was dried at 120℃for 260 minutes. And (3) placing the dried sample into a muffle furnace, and roasting at a constant temperature of 800 ℃ at a heating rate of 3.5 ℃/min to obtain the carrier Z-5.
The cross-sectional shape of the obtained carrier Z-5 particles is clover-shaped, and the diameter of the circumcircle of the particles is 3.0mm. The carrier properties are as follows: specific surface area of 210m 2 Per g, pore volume of 0.84cm 3 And/g. The water absorption was 1.15.
13.1g of molybdenum trioxide (containing 99wt percent of molybdenum oxide), 4.8g of basic nickel carbonate (containing 54wt percent of nickel oxide) and 5.0g of phosphoric acid solution (containing 26.7wt percent of phosphorus) are accurately weighed, put into a beaker according to a certain sequence, added with purified water, reacted for 40 minutes at normal temperature, added with 3.6g of tartaric acid, and continuously reacted for 35 minutes, and then heated and boiled until the raw materials are completely dissolved. After keeping the temperature for 70 minutes, the temperature is reduced to 25 ℃ and the volume is fixed to 110mL for standby. 100g of Z-6 carrier is weighed, and the obtained impregnating solution is fully mixed with the carrier Z-6 by adopting a spraying method. The sample after the complete homogenization treatment is placed in a closed container at room temperature for 4.0 hours, then dried at 125 ℃ for 2.5 hours, and finally baked at 570 ℃ for 3.0 hours to prepare the catalyst ZC-5.
Comparative example 1
700g of pseudo-boehmite containing phosphorus (1 wt%) and 10g of hydroxypropyl methylcellulose, 30g of carbon black and 890g of deionized water are weighed. Mixing the materials, adding into a kneader, forming a plastic body through a kneading operation unit, and obtaining the granular material with the shape of four-leaf grass through an extrusion molding method. After molding, the granular material was dried at 130℃for 240 minutes. And (3) placing the dried sample into a muffle furnace, and roasting at a constant temperature of 800 ℃ and under a certain atmosphere at a heating rate of 3.5 ℃/min to obtain the carrier Z-6.
The cross-sectional shape of the obtained carrier Z-6 particles is clover-shaped, and the long axis of the cross section of the particles is 2.8 mm. The carrier properties are as follows: specific surface area of 190m 2 Per g, pore volume of 0.79cm 3 And/g. The water absorption was 1.09.
11.9g of molybdenum trioxide (containing 99wt percent of molybdenum oxide), 4.3g of basic nickel carbonate (containing 54wt percent of nickel oxide) and 4.1g of phosphoric acid solution (containing 26.7wt percent of phosphorus) are accurately weighed, put into a beaker according to a certain sequence, added with purified water, reacted for 30 minutes at normal temperature, added with 4.3g of citric acid, and continuously reacted for 35 minutes, and then heated and boiled until the raw materials are completely dissolved. Keeping the temperature for 60 minutes, and then cooling to 25 ℃ for standby. Slowly adding a mixture of 8.1g of hexamethylenetetramine and 3.0g of tween-60 into the solution under stirring, stirring until the solution becomes clear, maintaining the stirring state for 40 minutes, stopping, and fixing the volume to 115mL for later use. 100g of Z-5 carrier is weighed, and the obtained impregnating solution is fully mixed with the carrier Z-5 by adopting a spraying method. The sample after the complete homogenization treatment is placed under a closed container at room temperature for 6.0 hours, then dried at 130 ℃ for 3 hours, and finally baked at 560 ℃ for 3.0 hours to prepare the catalyst ZC-6.
Comparative example 2
700g of pseudo-boehmite without auxiliary agent, 10g of hydroxypropyl methylcellulose, 25g of carbon black and 900g of deionized water are weighed. Mixing the materials, adding into a kneader, forming a plastic body through a kneading operation unit, and obtaining the granular material with the shape of four-leaf grass through an extrusion molding method. After molding, the granular material was dried at 130℃for 250 minutes. And (3) placing the dried sample into a muffle furnace, and roasting at a constant temperature of 810 ℃ and under a certain atmosphere at a heating rate of 4.0 ℃/min to obtain the carrier Z-7.
The cross-sectional shape of the obtained carrier Z-7 particles is clover-shaped, and the long axis of the cross section of the particles is 3.0mm. The carrier properties are as follows: specific surface area of 180m 2 Per g, pore volume of 0.76cm 3 And/g. The water absorption was 1.01.
12.9g of molybdenum trioxide (containing 99wt% of molybdenum oxide) and 4.4g of basic nickel carbonate (containing 54wt% of nickel oxide) are accurately weighed, put into a beaker according to a certain sequence, added with purified water, reacted for 30 minutes at normal temperature, added with 5.6g of citric acid, continuously reacted for 40 minutes, and heated and boiled until the raw materials are completely dissolved. Keeping the temperature for 60 minutes, and then cooling to 25 ℃ for standby. Slowly adding 8.1g of hexamethylene tetramine and 2.5g of tween-60 mixture into the solution under stirring, stirring until the solution becomes clear, maintaining the stirring state for 40 minutes, stopping, and fixing the volume to 105mL for later use. 100g of Z-7 carrier is weighed, and the obtained impregnating solution is fully mixed with the carrier Z-7 by adopting a spraying method. The sample after the complete homogenization treatment is placed under a room temperature closed container for 5.0 hours, then dried for 2.5 hours at 120 ℃, and finally baked for 3.0 hours at 580 ℃ to prepare the catalyst ZC-7.
Table 1 composition and properties of the catalysts of examples and comparative examples
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Shape and shape | Clover with three leaves | Clover with three leaves | Clover with three leaves | Clover with three leaves | Clover with three leaves | All-grass of Sileaf Mesona | All-grass of Sileaf Mesona |
| Particle diameter/mm | 3.0 | 2.6 | 2.0 | 2.5 | 3.0 | 2.8 | 3.0 |
| Void fraction/% | 47.3 | 46.9 | 46.1 | 46.4 | 47.3 | 43.1 | 43.2 |
| Active ingredient content | |||||||
| MoO 3 ，wt% | 10.1 | 9.3 | 12.0 | 11.4 | 10.9 | 10.1 | 10.8 |
| NiO，wt% | 2.0 | 2.0 | 2.6 | 2.3 | 2.2 | 2.0 | 2.1 |
| Properties of (C) | |||||||
| Specific surface area, m 2 /g | 178 | 148 | 151 | 157 | 168 | 157 | 145 |
| Pore volume, cm 3 /g | 0.68 | 0.64 | 0.58 | 0.63 | 0.61 | 0.62 | 0.60 |
| Pore diameter, nm | 15.3 | 17.3 | 15.4 | 16.8 | 14.5 | 15.8 | 16.5 |
Table 2 comparison of hydrogenation performance of examples and comparative examples
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Raw oil | Residuum | Residuum | Residuum | Residuum | Residuum | Residuum | Residuum |
| S/µg·g -1 | 3.7 | 3.7 | 3.7 | 3.7 | 3.7 | 3.7 | 3.7 |
| Ni+V/µg·g -1 | 90 | 90 | 90 | 90 | 90 | 90 | 90 |
| Asphaltenes/wt% | 4.6 | 4.6 | 4.6 | 4.6 | 4.6 | 4.6 | 4.6 |
| Reaction pressure, MPa | 15.7 | 15.7 | 15.7 | 15.7 | 15.7 | 15.7 | 15.7 |
| Reaction temperature, DEG C | 379 | 380 | 384 | 382 | 383 | 381 | 385 |
| Volume space velocity，h -1 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Hydrogen to oil ratio, V/V | 600 | 600 | 600 | 600 | 600 | 600 | 600 |
| Relative removal rate% | |||||||
| HDS | 116 | 110 | 121 | 120 | 110 | 105 | 100 |
| HDM | 134 | 122 | 139 | 136 | 107 | 107 | 100 |
| HDAs | 119 | 118 | 126 | 121 | 105 | 103 | 100 |
From the composition and evaluation result of the catalyst, the catalyst has higher bed void ratio, and can effectively relieve the rapid increase of pressure drop caused by coking among catalyst particles. The catalyst prepared by the method provided by the invention has overall performance superior to that of the catalyst of the comparative example. The reason for this is that there is a significant difference in the pore properties of the comparative example and the example catalysts. The catalyst carrier is mainly characterized in that after the catalyst carrier is modified, the hydrogenation performance is higher, which is beneficial to cracking asphaltene and colloid macromolecules into micromolecules and realizing hydrogenation conversion. Meanwhile, the larger pore diameter can reduce the diffusion resistance of asphaltene and colloid macromolecules in the pore canal of the catalyst, and the accessibility of reactants and reactive centers is improved, so that the reaction efficiency is improved.
Claims (14)
1. A heavy oil hydrotreating catalyst, characterized in that the catalyst comprises a carrier and an active metal component; the void ratio of the catalyst in dense phase filling is 46% -48%;
the catalyst is granular, the cross section of the granule is clover-shaped, and the diameter of the circumcircle of the granule is 2.0-3.5 mm;
the specific surface area of the catalyst is 130-180 m 2 /g; the pore volume is 0.55-0.70 cm 3 /g; the average pore diameter is 15 nm-20 nm;
the catalyst is prepared by a preparation method comprising the following steps:
(1) Preparing a catalyst carrier: taking pseudo-boehmite, adding a pore-enlarging agent and an adhesive, kneading, forming, drying and roasting to obtain a catalyst carrier;
(2) Preparing an active metal impregnating solution containing an auxiliary agent: preparing an active metal impregnating solution, wherein the impregnating solution contains phosphorus and/or boron, and the content of the active metal impregnating solution is 10-90 g/L in terms of phosphorus and/or boron;
(3) Impregnating the carrier in the step (1) with the impregnating solution in the step (2), and drying and roasting to obtain a hydrotreating catalyst;
in the step (1), pseudo-boehmite is produced by adopting an aluminum sulfate method, and auxiliary agents phosphorus and/or boron are added, wherein the content of the phosphorus and/or the boron is 0.5% -5.0% by weight of the carrier;
the pore-expanding agent in the step (1) is one or more of carbon black, methylcellulose, sesbania powder, polyethylene glycol and starch; the adhesive is a neutral adhesive;
adding an amine compound into the impregnating solution in the step (2); the amine compound is one or more of hexamethylenetetramine, ethylenediamine, octylamine, methanolamine, dimethanol amine, trimethanolamine, propanolamine, dipropanolamine, tripropanolamine, polyalcohol amine, ethanolamine, diethanolamine and triethanolamine;
adding a surfactant into the impregnating solution in the step (2), wherein the surfactant is one or more of Tween-20, tween-30, tween-40, tween-60, tween-80 and Tween-85;
adding an organic acid compound into the impregnating solution in the step (2), wherein the organic acid is one or more of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid and malic acid.
2. The catalyst according to claim 1, wherein the content of phosphorus and/or boron in the step (1) is 0.7% -3.0% by weight of the carrier.
3. The catalyst according to claim 1, wherein in the step (2), the content is 20 to 70g/L in terms of phosphorus and/or boron.
4. A process for preparing the catalyst of any one of claims 1 to 3, comprising the steps of:
(1) Preparing a catalyst carrier: taking pseudo-boehmite, adding a pore-enlarging agent and an adhesive, kneading, forming, drying and roasting to obtain a catalyst carrier;
(2) Preparing an active metal impregnating solution containing an auxiliary agent: preparing an active metal impregnating solution, wherein the impregnating solution contains phosphorus and/or boron, and the content of the active metal impregnating solution is 10-90 g/L in terms of phosphorus and/or boron;
(3) Impregnating the carrier in the step (1) with the impregnating solution in the step (2), and drying and roasting to obtain a hydrotreating catalyst;
in the step (1), pseudo-boehmite is produced by adopting an aluminum sulfate method, and auxiliary agents of phosphorus and/or boron are added, wherein the content of the phosphorus and/or the boron is 0.5% -5.0% by weight of the carrier.
5. The method of claim 4, wherein the pore-expanding agent in step (1) is one or more of sesbania powder, methylcellulose and carbon black.
6. The method of claim 4, wherein the adhesive in step (1) is hydroxypropyl methylcellulose.
7. The method according to claim 4, wherein the amine compound is contained in the impregnating solution in an amount of 6g/L to 20 g/L.
8. The method according to claim 7, wherein the amine compound is contained in the impregnating solution in an amount of 8g/L to 15g/L.
9. The method according to claim 4, wherein the surfactant in the step (2) is tween-60 and/or tween-80.
10. The method according to claim 4, wherein the content of the surfactant in the impregnating solution is 2 to 80/L.
11. The preparation method of claim 10, wherein the content of the surfactant in the impregnating solution is 5-50 g/L.
12. The method according to claim 4, wherein the organic acid in the step (2) is citric acid.
13. The method according to claim 4, wherein the content of the organic acid compound in the impregnating solution is 2 to 120 g/L.
14. The method according to claim 13, wherein the content of the organic acid compound in the impregnating solution is 4 to 50g/L.
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