CN112705212B - Regeneration method of deactivated residuum hydrotreatment catalyst - Google Patents
Regeneration method of deactivated residuum hydrotreatment catalyst Download PDFInfo
- Publication number
- CN112705212B CN112705212B CN201911023174.9A CN201911023174A CN112705212B CN 112705212 B CN112705212 B CN 112705212B CN 201911023174 A CN201911023174 A CN 201911023174A CN 112705212 B CN112705212 B CN 112705212B
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- Prior art keywords
- catalyst
- regeneration method
- carrying
- phosphonic acid
- deactivated
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 151
- 238000011069 regeneration method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 239000012670 alkaline solution Substances 0.000 claims abstract description 13
- 238000005470 impregnation Methods 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 10
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 239000003929 acidic solution Substances 0.000 claims abstract description 5
- 239000003610 charcoal Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 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
- 230000008569 process Effects 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 229940120146 EDTMP Drugs 0.000 claims description 5
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000008213 purified water Substances 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 2
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 23
- 239000011148 porous material Substances 0.000 abstract description 15
- 150000002739 metals Chemical class 0.000 abstract description 13
- 239000012492 regenerant Substances 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000002699 waste material Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910003294 NiMo Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/08—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using ammonia or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
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- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C10G2300/202—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
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- C10G2300/205—Metal content
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a regeneration method of an inactivated residuum hydrotreating catalyst. The method comprises the following steps: the method comprises the steps of carrying out charcoal burning and sulfur removal pretreatment on an inactivated residual oil hydrotreating catalyst, carrying out ultrasonic treatment, carrying out unsaturated impregnation or saturated impregnation by an acidic solution containing organic phosphonic acid, carrying out impregnation treatment by an alkaline solution, carrying out heat treatment in an ammonia-containing atmosphere, and carrying out drying and roasting to obtain the regenerated hydrotreating catalyst. The method fully utilizes the deposited metal impurities, so that the deposited metal impurities are used as active metals in the regenerated catalyst, the loss of the active metals is reduced, the pore structure of the catalyst is improved, and the catalyst has higher specific surface and pore volume, so that the regenerated catalyst has good activity and stability and can be equivalent to fresh catalyst.
Description
Technical Field
The present invention relates to a method for regenerating deactivated catalyst produced in petroleum refining process, in particular, it is a method for regenerating hydrotreatment catalyst deactivated by deposition of metal impurity of nickel, vanadium and iron, etc..
Background
During the hydrogenation reaction, the activity of the catalyst gradually decreases with the increase of the running time and eventually becomes inactive. There are many factors that cause catalyst deactivation, with coke deposition being the predominant one. Coke is often deposited on the catalyst surface to block the channels and cover the active sites of the catalyst, thereby reducing the reactivity. Deactivated spent catalyst is typically used after regeneration recovery activity is required, whereas spent catalyst that is not recovered by regeneration is discarded as solid waste. Most of the refinery catalyst waste originates from residuum hydrotreaters because the deactivated catalyst produced by such a unit, in addition to coke deposition, has severe plugging of orifices and channels due to progressive deposition of metallic (vanadium, nickel, iron, etc.) impurities, which can exceed 20% by weight of the spent catalyst. Although deactivation by coke can be eliminated by calcination treatment in an oxygen-containing atmosphere, deactivation by metal deposition clogging cannot be removed by the oxygen-containing atmosphere calcination method.
The recovery of high value metals from spent catalyst, while reasonably utilizing resources and having considerable economic benefits, clearly adds additional energy consumption. If the heavy oil hydrotreating waste catalyst can be directly regenerated, the heavy oil hydrotreating waste catalyst can be partially or completely replaced by a fresh catalyst, and the heavy oil hydrotreating waste catalyst has important practical significance in increasing economic benefits of refineries, reducing energy consumption and reducing environmental pollution.
The treatment of the waste catalyst is mainly focused on recycling metals in the waste catalyst, so that not only can the active metal resources be recycled, but also the pollution of the active metal resources to the environment can be reduced. However, the existing waste catalyst metal recovery technology has the common problems that the metal recovery rate is low, and the rest of metal and waste slag are discharged together, so that resource waste is formed to a certain extent and the environment is polluted. CN1258754a discloses a method for recovering metals from Co-Mo-based spent catalysts. The method comprises the steps of roasting, crushing, ammonolysis and filtering the waste catalyst, replacing cobalt in the complex with zinc, and then adding nitric acid to recycle MoO 3 The filter residue was dissolved with sulfuric acid and ammonium alum was separated with ammonium sulfate to remove most of the aluminum. CN1752021a discloses a method for producing vanadium pentoxide by using a vanadium-containing spent catalyst. The method is characterized in that after the deposited oil in the catalyst is removed, the catalyst is crushed, and sodium vanadate and sodium molybdate are recovered through oxidation and alkali treatment. And adding excessive ammonium chloride into the leaching solution to enable sodium vanadate to generate ammonium metavanadate, and decomposing at 800-850 ℃ to generate molten vanadium pentoxide.
Because heavy oil and residual oil contain a large amount of metal impurities such as nickel, vanadium, iron and the like, the heavy oil and residual oil are easy to deposit in a hydrotreating catalyst in the hydrotreating process, so that the hydrotreating catalyst is deactivated. At present, how to remove the deposited metal impurities in the deactivated residual oil hydrotreating catalyst and restore the pore structure and activity of the catalyst is still an important research topic.
CN102451774B discloses a method for regenerating an inactivated hydrotreating catalyst. The method comprises the following steps: the method for removing the metal impurities deposited in the deactivated catalyst comprises the steps of soaking the deactivated hydrotreating catalyst in alkaline solution, filtering, and then pickling the filtered solid. The method is that firstly, alkaline solution is used to treat the metal impurities of vanadium, nickel and iron to form precipitate, and then the removed metals of vanadium, nickel and iron are washed out from the catalyst pore channels by acid washing method, so as to recover the catalyst pore channels blocked by the metal deposition of vanadium, nickel and iron. The process may reduce the activity of the catalyst by losing part of the active metal during regeneration.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a regeneration method of an inactivated residual oil hydrotreating catalyst. The method fully utilizes the deposited metal impurities, so that the deposited metal impurities are used as active metals in the regenerated catalyst, the loss of the active metals is reduced, the pore structure of the catalyst is improved, and the catalyst has higher specific surface and pore volume, so that the regenerated catalyst has good activity and stability and can be equivalent to fresh catalyst.
The invention provides a regeneration method of an inactivated residual oil hydrotreating catalyst, which comprises the following steps:
(1) The inactivated residuum hydrotreatment catalyst is subjected to carbon burning and sulfur removal pretreatment,
(2) Carrying out ultrasonic treatment on the catalyst obtained in the step (1),
(3) Unsaturated impregnating or saturating the catalyst obtained in the step (2) with an acidic solution containing an organic phosphonic acid,
(4) Impregnating the catalyst obtained in the step (3) with an alkaline solution, then carrying out heat treatment in an ammonia-containing atmosphere, and drying and roasting to obtain the regenerated hydrotreating catalyst.
In the step (1), the pretreatment of burning charcoal and removing sulfur on the deactivated hydrotreating catalyst can be carried out by adopting a conventional method. The charcoal-burning sulfur removal treatment process can be carried out for 2-10 hours at 200-500 ℃ in an air atmosphere, preferably two-stage heat treatment is adopted, the first stage is constant-temperature roasting for 2-4 hours at 200-300 ℃, preferably 220-250 ℃, and the second stage is constant-temperature roasting for 2-4 hours at 350-450 ℃, preferably 400-430 ℃. The heating rate in the heat treatment process is 2-6 ℃/min.
In the step (2), the ultrasonic treatment process is as follows: and (3) placing the catalyst obtained in the step (1) into an ultrasonic generator, wherein the medium is water, and performing ultrasonic treatment under certain conditions. Wherein, the ultrasonic treatment conditions are as follows: the temperature is 20-70 ℃, the ultrasonic frequency is 10-150 KHz, the treatment time is 10-120 minutes, and the preferable conditions are as follows: the temperature is 25-50 ℃, the ultrasonic frequency is 15-80 KHz, and the treatment time is 20-80 minutes.
And (3) drying the catalyst obtained after the ultrasonic treatment in the step (2), and then carrying out the step (3). The drying conditions are as follows: drying at 50-120 ℃ for 1-10 hours.
In the step (3), the acid solution is a citric acid and/or oxalic acid solution, and the concentration of the acid solution is 2-20wt%, preferably 6-16wt%, and more preferably 8-16wt%; the organic phosphonic acid is one or more of amino trimethylene phosphonic acid, hydroxy ethylene diphosphonic acid, ethylenediamine tetramethylene phosphonic acid, diamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid and hexamethylenediamine tetramethylene phosphonic acid. The concentration of the organic phosphonic acid is 5-25 wt%, preferably 6-20 wt%.
In the step (3), the amount of the unsaturated impregnating solution is more than 70% of the saturated water absorption amount of the catalyst obtained in the step (2). The amount of the saturated impregnating solution used in the saturated impregnation is 100% of the saturated water absorption of the catalyst obtained in the step (2). Step (3) is preferably saturated impregnation, i.e. isovolumetric impregnation.
The dipping in the step (3) can be processed by homogenization, or can be kept stand for a certain time and then the operation of the step (4) is carried out. Wherein the standing time is generally 0.5-3.0 hours.
In the step (4), the alkaline solution is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, potassium carbonate and potassium bicarbonate, preferably ammonium carbonate or sodium carbonate solution, and the concentration of the alkaline solution is 5wt% to 30wt%, preferably 10wt% to 25wt%.
In the step (4), the amount of the impregnating solution adopted in the impregnation is 30% -100% of the saturated water absorption amount of the catalyst obtained in the step (2).
In the step (4), after the catalyst obtained in the step (3) is impregnated with the alkaline solution, the catalyst may be allowed to stand for a period of time, which may be 0.5 to 3.0 hours.
In the step (4), the heat treatment is performed under a closed condition in the ammonia-containing atmosphere, wherein the ammonia-containing atmosphere is derived from ammonium bicarbonate and/or ammonia, the volume fraction of the ammonia is 5-15 wt%, and the balance can be at least one of inert gas, nitrogen, water vapor or carbon dioxide. The heat treatment conditions are as follows: the temperature is 50-100 ℃, and the treatment time is 0.3-3.0 hours.
In the step (4), after the heat treatment under an ammonia-containing atmosphere, the process of separation by filtration and washing is preferable before the drying and baking are performed. And (3) taking the saturated water absorption amount of the catalyst obtained in the step (2) as a basis, wherein the volume of the purified water washed each time accounts for 80% -120% of the saturated water absorption amount of the catalyst obtained in the step (2), and the washing times are 1-3.
In the step (4), the drying and roasting conditions are as follows: drying at 70-120 ℃ for 1-5 hours, and roasting at 450-650 ℃ for 1-5 hours.
The active metal lost in the regeneration process of the present invention can be replenished by impregnation to further restore the activity of the catalyst.
The residual oil hydrotreating catalyst of the present invention is mainly used in the hydrotreating process of heavy oil and residual oil. The residuum hydrotreatment catalyst generally takes alumina as a carrier, and VIB and/or VIII metals as hydrogenation active metal components. The VIB metal is at least one of Mo and W. The VIII group metal is at least one of Ni and Co. The deactivated residuum hydrotreating catalyst is a hydrotreating catalyst deactivated by deposition of coke and deposition of metal impurities such as nickel, vanadium, iron, etc. Deactivated hydrotreating catalysts typically contain deposited metal impurities such as vanadium, nickel, and iron. In the conventional deactivated residuum hydrotreating catalyst, the deposition amount of vanadium is 0.5wt% to 20.0wt%, the deposition amount of nickel is 0.5wt% to 10.0wt% and the deposition amount of iron is 0.2wt% to 5.0wt% based on the weight of the deactivated hydrotreating catalyst.
Compared with the prior art, the method has the following advantages:
after the carbon is burnt to remove sulfur, the method adopts an ultrasonic method to treat the iron-containing substances attached to the surfaces of the catalyst particles, reduces the load of the subsequent chemical treatment process, then firstly uses an acid solution containing organic phosphonic acid to impregnate, so that partial aggregated active metals, impurity nickel, iron and the like react and redistribute in catalyst pore channels, and is favorable for recovering and improving the activity of the catalyst in the subsequent improvement process, then, the alkali solution is impregnated and then treated in an ammonia-containing atmosphere, thereby promoting the redistribution of vanadium on the outer surface and near surface of the catalyst, improving the pore channel structure of the catalyst, further promoting the uniform distribution of the active metals, further regenerating the deactivated hydrotreating catalyst, and basically achieving the performance of a fresh agent.
The method fully utilizes the deposited metal impurities, so that the deposited metal impurities are used as active metals in the regenerated catalyst, the loss of the active metals is reduced, the pore structure of the catalyst is improved, and the catalyst has higher specific surface and pore volume, so that the regenerated catalyst has good activity and stability and can be equivalent to fresh catalyst.
The method has the advantages that the obtained regenerated catalyst can partially or completely replace fresh catalyst, thereby improving the utilization value of the deactivated catalyst and saving the cost of the catalyst.
Detailed Description
The method of the present invention will be described in detail with reference to the following specific examples, but is not intended to limit the scope of the present invention. The weight percent is the mass fraction.
Example 1
Taking 100g of an industrial operation post-deactivation residual oil hydrotreating catalyst which is NiMo/Al 2 O 3 I.e. the deactivator A-1. And (3) placing the deactivator A-1 into a high-temperature furnace for roasting heat treatment. The heating rate is 3 ℃/min, and the temperature is kept at 230 ℃ for 3 hours; and keeping the temperature at 420 ℃ for 3 hours to obtain the catalyst A-2. Will catalyzeThe catalyst A-2 is put into an ultrasonic generator, treated for 30 minutes at the temperature of 30 ℃ and the ultrasonic frequency of 50KHz by taking water as a medium, and dried for 90 minutes at the temperature of 100 ℃ in a drying oven to obtain the catalyst A-3. The catalyst A-3 was placed in a rotary pot, and was sprayed with a citric acid solution containing aminotrimethylene phosphonic acid at room temperature by an unsaturated impregnation method (80% of saturated water absorption) for 10 minutes and homogenized for 30 minutes, and then taken out and left to stand for 1 hour to obtain a catalyst A-4. The concentration of the aminotrimethylene phosphonic acid in the citric acid liquid containing the aminotrimethylene phosphonic acid is 10 weight percent, and the concentration of the citric acid is 9 weight percent. The catalyst A-4 was impregnated with an ammonium carbonate solution in an amount of 40% of the saturated water absorption amount of the catalyst A-3, the concentration of the ammonium carbonate solution was 15% by weight, and after standing at room temperature for 0.5 hours, it was further treated at 70℃for 0.8 hours under a mixed atmosphere of ammonia and nitrogen (ammonia volume concentration: 10%). Filtering and separating, and repeatedly washing the catalyst with the equal volume of purified water for 3 times to obtain the catalyst A-5. The generated precipitate and the washing liquid are collected and the metal component is recovered. And drying the catalyst A-5 at 80 ℃ for 2 hours, and then placing the catalyst A-5 into a high-temperature furnace for roasting. The temperature rising rate is 3 ℃/min, and the regenerant A-6 is obtained after the temperature is kept at 450 ℃ for 2 hours, and the physicochemical properties of the regenerant A-6 are shown in the table 1.
TABLE 1 physicochemical Properties of the catalyst
| Project | Fresh agent A | Deactivator A-1 | Regenerant A-6 |
| Specific surface area/m 2 ·g -1 | 186 | 138 | 191 |
| Pore volume/cm 3 ·g -1 | 0.48 | 0.35 | 0.52 |
| Composition/wt% | |||
| Mo | 10.1 | 7.8 | 9.0 |
| Ni | 2.7 | 4.3 | 4.6 |
| V | 0 | 1.9 | 1.6 |
| Fe | 0 | 0.72 | 0.31 |
The activity evaluation experiment of the regenerated catalyst was performed on a 200mL residuum hydrotreater, and the physicochemical properties and reaction conditions of the raw materials used are shown in Table 2. The results of the catalyst activity evaluation after regeneration are shown in Table 3.
TABLE 2 raw oil Properties and reaction conditions
| Project | Properties of (C) |
| S/wt% | 2.3 |
| Ni/μg·g -1 | 29.1 |
| V/μg·g -1 | 48.6 |
| Reaction conditions | |
| Temperature/. Degree.C | 382 |
| pressure/MPa | 15.8 |
| Liquid hourly space velocity/h -1 | 1.0 |
| Hydrogen to oil volume ratio | 700 |
TABLE 3 evaluation of regenerated catalyst Activity
| Removal rate | Fresh agent A | Regenerant A-6 | Regenerant DA-1 | Regenerant DA-2 | Regenerant DA-3 |
| HDS，% | 60.06 | 59.33 | 30.08 | 49.67 | 53.14 |
| HD(Ni+V)，% | 69.81 | 70.15 | 39.54 | 60.28 | 62.36 |
As can be seen from tables 1-3, the regenerant A-6 pore structure obtained by the method of the present invention was better recovered. The activity evaluation result shows that the desulfurization and demetallization activity of the regenerant A-6 is superior to that of the regenerants DA-1, DA-2 and DA-3, and is equivalent to that of the fresh agent A.
Example 2
Taking 100g of an industrial operation post-deactivation residual oil hydrotreating catalyst which is NiMo/Al 2 O 3 I.e. the deactivator A-1. And (3) placing the deactivator A-1 into a high-temperature furnace for roasting heat treatment. The heating rate is 3 ℃/min, and the temperature is kept at 240 ℃ for 3 hours; after 4 hours of constant temperature of 410 ℃, catalyst B-2 is obtained. Putting the catalyst B-2 into an ultrasonic generator, treating the catalyst B-2 with water as a medium at 40 ℃ and ultrasonic frequency of 60KHz for 45 minutes, and drying the catalyst B-3 in a drying oven at 100 ℃ for 90 minutes to obtain the catalyst B-3. The catalyst B-3 was placed in a rotary pot, and was sprayed with an oxalic acid solution containing ethylenediamine tetramethylene phosphonic acid at room temperature by an unsaturated impregnation method (90% of saturated water absorption) for 10 minutes and homogenized for 30 minutes, and then taken out and left to stand for 1 hour to obtain the catalyst B-4. In the oxalic acid solution containing ethylenediamine tetramethylene phosphonic acid, the content of ethylenediamine tetramethylene phosphonic acid is 15wt percent, and the content of oxalic acid is 10wt percent. Putting the catalyst B-3 into an equal volume of catalyst B-4 impregnated with a sodium carbonate solution, wherein the dosage of the sodium carbonate solution is 35% of the saturated water absorption capacity of the catalyst B-3, the concentration of the sodium carbonate solution is 12% by weight, standing for 1 hour at room temperature, then treating for 1.5 hours at 60 ℃ under the mixed atmosphere of ammonia and nitrogen (the volume concentration of ammonia is 8%), filtering and separating, and repeatedly washing the catalyst with equal volume of purified water for 3 times to obtain the catalyst B-5. The generated precipitate and the washing liquid are collected and the metal component is recovered. And drying the catalyst B-5 at 80 ℃ for 2 hours, and then placing the catalyst B-5 into a high-temperature furnace for roasting. The temperature rising rate is 3 ℃/min, and the regenerant B-6 is obtained after the temperature is kept at 450 ℃ for 2 hours, and the physicochemical properties of the regenerant B-6 are shown in Table 4.
TABLE 4 physicochemical Properties of the catalyst
| Project | Fresh agent A | Deactivator A-1 | Regenerant B-6 |
| Specific surface area/m 2 ·g -1 | 186 | 138 | 195 |
| Pore volume/cm 3 ·g -1 | 0.48 | 0.35 | 0.53 |
| Composition/wt% | |||
| Mo | 10.1 | 7.8 | 8.6 |
| Ni | 2.7 | 4.3 | 4.6 |
| V | 0 | 1.9 | 1.5 |
| Fe | 0 | 0.72 | 0.29 |
The activity evaluation experiment of the regenerated catalyst was performed on a 200mL residuum hydrotreater, and the physicochemical properties and reaction conditions of the raw materials used are shown in Table 5. The results of the catalyst activity evaluation after regeneration are shown in Table 3.
TABLE 5 raw oil Properties and reaction conditions
| Project | Properties of (C) |
| S/wt% | 2.8 |
| Ni/μg·g -1 | 25.3 |
| V/μg·g -1 | 43.6 |
| Reaction conditions | |
| Temperature/. Degree.C | 385 |
| pressure/MPa | 16.0 |
| Liquid hourly space velocity/h -1 | 1.0 |
| Hydrogen to oil volume ratio | 700 |
TABLE 6 evaluation of regenerated catalyst Activity
| Removal rate | Fresh agent A | Regenerant B-6 |
| HDS，% | 62.54 | 61.92 |
| HD(Ni+V)，% | 70.03 | 71.81 |
As can be seen from tables 4-6, the pore structure of regenerant B-6 obtained by the method of the present invention was better recovered. The activity evaluation result shows that the desulfurization and demetallization activity of the regenerant B-6 is equivalent to that of the fresh agent A.
Comparative example 1
Catalyst A-4 of example 1 was repeatedly washed 3 times with an equal volume of purified water to obtain a catalyst. Drying at 80 deg.c for 2 hr, and roasting in a high temperature furnace. The temperature rising rate is 3 ℃/min, and the regenerant DA-1 is obtained after the temperature is kept at 450 ℃ for 2 hours. The physicochemical properties of the starting materials used and the reaction conditions are shown in Table 2. The results of the catalyst activity evaluation after regeneration are shown in Table 3.
Comparative example 2
In comparison with example 1, the citric acid solution containing aminotrimethylene phosphonic acid was replaced with an aminotrimethylene phosphonic acid solution containing no citric acid to obtain a regenerant DA-2. The physicochemical properties of the starting materials used and the reaction conditions are shown in Table 2. The results of the catalyst activity evaluation after regeneration are shown in Table 3.
Comparative example 3
Compared with example 1, the ammonia-containing gas heat treatment process was omitted after immersing and standing in the ammonium carbonate solution, to obtain a regenerant DA-3. The physicochemical properties of the starting materials used and the reaction conditions are shown in Table 2. The results of the catalyst activity evaluation after regeneration are shown in Table 3.
Example 3
This example is a catalyst stability evaluation test.
The evaluation results after 1200 hours of operation using the same raw materials and operating conditions (raw materials and operating conditions are shown in Table 2) for the fresh agent A and the catalyst A-6 are shown in Table 7.
TABLE 7 evaluation results of stability of catalysts
| Removal rate | Fresh agent A | Regenerant A-6 |
| HDS，% | 59.87 | 59.01 |
| HD(Ni+V)，% | 68.79 | 69.81 |
As can be seen from Table 7, the regenerant A-6 obtained by the method of the present invention was comparable to fresh agent A in desulfurization and demetallization activity after 1200 hours of operation.
Claims (16)
1. A process for regenerating an deactivated residuum hydroprocessing catalyst comprising:
(1) The inactivated residuum hydrotreatment catalyst is subjected to carbon burning and sulfur removal pretreatment,
(2) Carrying out ultrasonic treatment on the catalyst obtained in the step (1),
(3) Unsaturated impregnating or saturating the catalyst obtained in the step (2) with an acidic solution containing an organic phosphonic acid,
(4) Impregnating the catalyst obtained in the step (3) with an alkaline solution, then performing heat treatment in an ammonia-containing atmosphere, and drying and roasting to obtain a regenerated hydrotreating catalyst;
the deactivated residual oil hydrotreating catalyst is a hydrotreating catalyst deactivated by coke deposition and metal impurity deposition; the deactivated hydrotreating catalyst contains deposited metal impurities of vanadium, nickel and iron;
in the step (1), the process of carrying out charcoal burning and sulfur removal pretreatment on the deactivated hydrotreating catalyst adopts two-stage heat treatment, wherein the first stage is roasting at the constant temperature of 200-300 ℃ for 2-4 hours, the second stage is roasting at the constant temperature of 350-450 ℃ for 2-4 hours, and the heating rate in the heat treatment process is 2-6 ℃/min;
in the step (3), the acidic solution is citric acid and/or oxalic acid solution; the organic phosphonic acid is one or more of amino trimethylene phosphonic acid, hydroxy ethylene diphosphonic acid, ethylenediamine tetramethylene phosphonic acid, diamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid and hexamethylenediamine tetramethylene phosphonic acid;
in the step (3), the concentration of the acid solution is 2-20wt%; the concentration of the organic phosphonic acid is 5-25 wt%;
in the step (4), the alkaline solution is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, potassium carbonate and potassium bicarbonate;
in the step (4), the amount of the impregnating solution adopted in the impregnation is 30% -100% of the saturated water absorption amount of the catalyst obtained in the step (2);
in the step (4), the drying and roasting conditions are as follows: drying at 70-120 deg.c for 1-5 hr and roasting at 450-650 deg.c for 1-5 hr; the heat treatment conditions are as follows: the temperature is 50-100 ℃, and the treatment time is 0.3-3.0 hours.
2. A regeneration method according to claim 1, characterized in that: in the step (1), the process of carrying out the charcoal burning and sulfur removal pretreatment on the deactivated hydrotreating catalyst adopts two-stage heat treatment, wherein the first stage is at 220-250 ℃ and the second stage is at 400-430 ℃.
3. A regeneration method according to claim 1, characterized in that: in the step (2), the conditions of the ultrasonic treatment are as follows: the temperature is 20-70 ℃, the ultrasonic frequency is 10-150 KHz, and the treatment time is 10-120 minutes.
4. A regeneration method according to claim 3, characterized in that: in the step (2), the conditions of the ultrasonic treatment are as follows: the temperature is 25-50 ℃, the ultrasonic frequency is 15-80 KHz, and the treatment time is 20-80 minutes.
5. A regeneration method according to claim 1, characterized in that: after the ultrasonic treatment in the step (2), drying the obtained catalyst, and then carrying out the step (3); the drying conditions are as follows: drying at 50-120 deg.c for 1-10 hr.
6. A regeneration method according to claim 1, characterized in that: in the step (3), the concentration of the acid solution is 6-16 wt%; the concentration of the organic phosphonic acid is 6-20wt%.
7. A regeneration method according to claim 1, characterized in that: in the step (3), the concentration of the acidic solution is 8-16 wt%.
8. A regeneration method according to claim 1, characterized in that: in the step (3), the dosage of the unsaturated impregnating solution is more than 70% of the saturated water absorption capacity of the catalyst obtained in the step (2); the amount of the saturated impregnating solution used in the saturated impregnation is 100% of the saturated water absorption of the catalyst obtained in the step (2).
9. A regeneration method according to claim 1, characterized in that: homogenizing after the dipping in the step (3), standing for a certain time, and then carrying out the operation of the step (4); wherein the standing time is 0.5-3.0 hours.
10. A regeneration method according to claim 1, characterized in that: in the step (4), the concentration of the alkaline solution is 5-30wt%.
11. The regeneration method according to claim 10, characterized in that: in the step (4), the alkaline solution is an ammonium carbonate or sodium carbonate solution.
12. The regeneration method according to claim 10, characterized in that: in the step (4), the concentration of the alkaline solution is 10-25 wt%.
13. A regeneration method according to claim 1, characterized in that: in the step (4), the catalyst obtained in the step (3) is immersed in an alkaline solution and then allowed to stand for a period of 0.5 to 3.0 hours.
14. A regeneration method according to claim 1, characterized in that: in the step (4), the heat treatment under the ammonia-containing atmosphere is performed under a closed condition, wherein the ammonia-containing atmosphere is derived from ammonium bicarbonate and/or ammonia, the volume fraction of the ammonia is 5-15 wt%, and the balance is at least one of inert gas, nitrogen, water vapor or carbon dioxide.
15. A regeneration method according to claim 1, characterized in that: in the step (4), after heat treatment under an ammonia-containing atmosphere, the process of filtering, separating and washing is carried out before drying and roasting; wherein, based on the saturated water absorption amount of the catalyst obtained in the step (2), the volume of the washing purified water in each time accounts for 80-120% of the saturated water absorption amount of the catalyst obtained in the step (2), and the washing times are 1-3 times.
16. A regeneration method according to claim 1, characterized in that: the deposition amount of vanadium is 0.5 to 20.0wt percent, the deposition amount of nickel is 0.5 to 10.0wt percent, and the deposition amount of iron is 0.2 to 5.0wt percent based on the weight of the deactivated hydrotreating catalyst.
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