CN111821998A - Treatment method of waste hydrogenation catalyst, hydrogenation catalyst obtained by treatment and application of hydrogenation catalyst - Google Patents
Treatment method of waste hydrogenation catalyst, hydrogenation catalyst obtained by treatment and application of hydrogenation catalyst Download PDFInfo
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- CN111821998A CN111821998A CN201910314031.7A CN201910314031A CN111821998A CN 111821998 A CN111821998 A CN 111821998A CN 201910314031 A CN201910314031 A CN 201910314031A CN 111821998 A CN111821998 A CN 111821998A
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- hydrogenation catalyst
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 183
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003921 oil Substances 0.000 claims abstract description 42
- 239000000295 fuel oil Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 17
- 239000003610 charcoal Substances 0.000 claims abstract description 12
- 239000012265 solid product Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 4
- 235000005985 organic acids Nutrition 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 56
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 39
- 229910052799 carbon Inorganic materials 0.000 claims description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000005470 impregnation Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 12
- 230000023556 desulfurization Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 description 15
- 239000012492 regenerant Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 229910003294 NiMo Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 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
- 230000009286 beneficial effect Effects 0.000 description 2
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- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
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- 238000007789 sealing Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/613—10-100 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
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of waste hydrogenation catalyst treatment, and discloses a treatment method of a waste hydrogenation catalyst, a hydrogenation catalyst obtained by treatment and application thereof, wherein the method comprises the following steps: 1) under oxygen-containing atmosphere, carrying out charcoal burning and hole expanding treatment on the waste hydrogenation catalyst, wherein the charcoal burning and hole expanding treatment comprises optional stages (1) and (2), and the conditions of the stage (1) comprise: the temperature is 200-500 ℃ and the time is 1-10 hours, and the conditions of the stage (2) comprise: the temperature is 500-850 ℃, and the time is 1-10 hours; 2) impregnating the solid product obtained in the step 1) with a solution containing an organic compound selected from at least one of organic alcohols, organic acids, organic amines and organic ammonium salts of C1-C20, and then drying. The hydrogenation catalyst obtained by the method for treating the waste hydrogenation catalyst provided by the invention is used in the heavy oil and/or residual oil hydrotreating process, and has better desulfurization and carbon residue removal performances.
Description
Technical Field
The invention relates to the field of waste hydrogenation catalyst treatment, in particular to a treatment method of a waste hydrogenation catalyst, a hydrogenation catalyst obtained by treatment and application of the hydrogenation catalyst.
Background
At present, each domestic refinery produces a large amount of waste distillate oil hydrogenation catalysts every year, and the waste catalysts are high in recovery and treatment cost and high in environmental protection pressure. If the waste catalysts can be applied after regeneration treatment, on one hand, the problem of recovery treatment of the waste catalysts can be solved, on the other hand, the cost of the existing hydrogenation catalyst can be greatly reduced, and the economic benefit is obvious.
In industrial production, the main reason for the deactivation of distillate oil hydrogenation catalysts is coke deposition, and for the deactivated catalysts, a common regeneration method is to firstly carry out carbon burning treatment on the catalysts under certain conditions, and then carry out active phase redispersion treatment on the carbon-burned catalysts by adopting a solution containing specific compound components.
CN1921942A reports a method for regenerating a deactivated hydrotreating catalyst, in which a hydrotreating catalyst deactivated by carbon deposition is first subjected to a carbon burning treatment under certain conditions to obtain an intermediate catalyst with a carbon content of 0.5-2.5 wt%, then the carbon-burned catalyst is contacted and aged with a nitrogen-containing chelating agent solution, and finally the regenerated catalyst is obtained by drying treatment.
CN106669866A discloses a regeneration method of a deactivated hydrogenation catalyst, which comprises the steps of carrying out charring treatment on the deactivated hydrogenation catalyst, then adopting a solution containing ammonium fluoborate and 2-amino-1, 3 propanediol to impregnate the charred catalyst, and carrying out heat treatment on the impregnated hydrogenation catalyst to obtain regeneration. The method can improve the specific surface area of the regenerated catalyst, promote the redispersion of the active components, ensure that the regenerated hydrogenation catalyst has high degree of vulcanization and improve the reaction activity.
Although the prior art is capable of achieving the treatment of spent hydrogenation catalysts, the reuse performance of the recovered catalyst is yet to be further improved.
Disclosure of Invention
The invention aims to overcome the problem that the performance of a regenerated waste hydrogenation catalyst in the prior art needs to be improved, and provides a treatment method of the waste hydrogenation catalyst, the hydrogenation catalyst obtained by treatment and application thereof.
In the research process, the inventor of the invention finds that the regenerated catalyst obtained by the existing recovery treatment method of the waste distillate oil hydrogenation catalyst can not meet the requirements of hydrogenation treatment on the performance of the catalyst when being used in the distillate oil hydrogenation treatment process again, for example, the activity and the selectivity can not completely meet the requirements, so that the effective recovery treatment of the waste distillate oil hydrogenation catalyst is limited. The inventor of the present invention changes the idea, and considers that the spent distillate hydrogenation catalyst is regenerated and then used in the heavy oil and/or residual oil hydrogenation process with slightly reduced catalyst requirements, but compared with the distillate oil, the heavy oil and/or residual oil raw material has higher molecular weight and larger molecular size of compounds, and the accessibility of the catalyst active center to macromolecular compounds in the heavy oil and/or residual oil needs to be increased, so as to improve the diffusion performance of catalyst pore channels, so the spent distillate oil hydrogenation catalyst cannot be directly used in the heavy oil and/or residual oil hydrogenation reaction after being regenerated. Therefore, upon conventional regeneration of the spent distillate hydrogenation catalyst, further treatment is required to make the regenerated distillate hydrogenation catalyst useful in heavy oil and/or residue hydrotreating processes.
In order to achieve the above object, a first aspect of the present invention provides a method for treating a spent hydrogenation catalyst, the method comprising:
1) under oxygen-containing atmosphere, carrying out charcoal burning and hole expanding treatment on the waste hydrogenation catalyst, wherein the charcoal burning and hole expanding treatment comprises optional stages (1) and (2), and the conditions of the stage (1) comprise: the temperature is 200-500 ℃ and the time is 1-10 hours, and the conditions of the stage (2) comprise: the temperature is 500-850 ℃, and the time is 1-10 hours;
2) impregnating the solid product obtained in the step 1) with a solution containing an organic compound selected from at least one of organic alcohols, organic acids, organic amines and organic ammonium salts of C1-C20, and then drying.
Preferably, the conditions of stage (1) include: treating at the temperature of 230-280 ℃ for 1-3 hours, and then treating at the temperature of 350-450 ℃ for 1-4 hours; the conditions of the stage (2) include: the temperature is 600 ℃ and 750 ℃ and the time is 1-4 hours.
The second aspect of the invention provides a hydrogenation catalyst obtained by the method for treating the waste hydrogenation catalyst, wherein the specific surface area of the catalyst is 80-250m2The pore volume is 0.2-0.9mL/g, and the most probable pore diameter is 5-14 nm.
In a third aspect, the present invention provides the use of a hydrogenation catalyst as described above in the hydroprocessing of heavy oils and/or residues.
Compared with the prior art, the hydrogenation catalyst obtained by the method for treating the waste hydrogenation catalyst can be applied to the hydrogenation reaction process of heavy oil and/or residual oil, and has better desulfurization and carbon residue removal effects.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the present invention, "optional" means "including or not including", "containing or not containing".
In a first aspect, the present invention provides a process for treating a spent hydrogenation catalyst, the process comprising:
1) under oxygen-containing atmosphere, carrying out charcoal burning and hole expanding treatment on the waste hydrogenation catalyst, wherein the charcoal burning and hole expanding treatment comprises optional stages (1) and (2), and the conditions of the stage (1) comprise: the temperature is 200-500 ℃ and the time is 1-10 hours, and the conditions of the stage (2) comprise: the temperature is 500-850 ℃, and the time is 1-10 hours;
2) impregnating the solid product obtained in the step 1) with a solution containing an organic compound selected from at least one of organic alcohols, organic acids, organic amines and organic ammonium salts of C1-C20, and then drying.
In the present invention, the spent hydrogenation catalyst refers to a catalyst whose performance (which may include at least one of activity, selectivity and stability) deteriorates after use, and includes both a spent hydrogenation catalyst that cannot meet the requirement of the activity of the hydrotreatment even after being regenerated by the existing means for a long period of time and a used hydrogenation catalyst that can be used again after being regenerated by the existing means. Because the spent hydrotreating catalyst has the characteristics of carbon deposit and/or high content of inactive metals (such as vanadium, sodium, iron and calcium) and the like relative to the fresh agent, the invention expresses whether the catalyst is the spent hydrotreating catalyst by the content of carbon and/or the content of inactive metals. Typically, the carbon content and the inactive metal content of the fresh agent are both substantially 0, whereas the carbon content of the spent hydrogenation catalyst may be as high as 30 wt.%, and the inactive metal content may even be as high as 50 wt.%.
According to a preferred embodiment of the present invention, the carbon content of the spent hydrogenation catalyst is less than 30 wt% and the inactive metal content is less than 20 wt%, further preferably the carbon content of the spent hydrogenation catalyst is less than 15 wt% and the inactive metal content is less than 10 wt%, further preferably the carbon content of the spent hydrogenation catalyst is 5-15 wt% and the inactive metal content is 1.5-10 wt%, based on the total amount of the spent hydrogenation catalyst.
In the present invention, unless otherwise specified, the carbon content of the spent hydrogenation catalyst is determined by a carbon-sulfur analyzer, and the content of the inactive metal is determined by X-ray fluorescence spectroscopy.
In the present invention, the spent hydrogenation catalyst may be any hydrogenation catalyst conventionally used for various oils in the art, and the present invention is not particularly limited thereto. According to an embodiment of the present invention, the spent hydrogenation catalyst of the present invention includes, but is not limited to, at least one of a spent gasoline hydrogenation catalyst, a spent diesel hydrogenation catalyst, a spent kerosene hydrogenation catalyst, and a spent wax oil hydrogenation catalyst. The embodiment of the invention is exemplified by a hydrogenation catalyst of waste diesel oil and a hydrogenation catalyst of waste wax oil.
According to the present invention, preferably, the spent hydrogenation catalyst comprises a carrier and a metal active component comprising molybdenum and/or tungsten and nickel and/or cobalt supported on the carrier. The content of molybdenum and/or tungsten and nickel and/or cobalt in the invention is selected widely, and can be adjusted by those skilled in the art according to the actual situation, and further preferably, based on the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst, the content of molybdenum and/or tungsten is 10-40 wt% and the content of nickel and/or cobalt is 1.5-8 wt% calculated by oxide. It should be noted that the spent hydrogenation catalyst contains the above-mentioned inactive metal and carbon deposited by long-term recycling, in addition to the carrier and the metal active component supported on the carrier. The phrase "based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst" as used herein means that the molybdenum and/or tungsten content and the nickel and/or cobalt content are based on fresh catalyst, i.e., the above-mentioned inactive metals and carbon are not included. The conventional selection ranges of the metal active components molybdenum and/or tungsten and nickel and/or cobalt in the waste gasoline hydrogenation catalyst, the waste diesel oil hydrogenation catalyst, the waste kerosene hydrogenation catalyst and the waste wax oil hydrogenation catalyst may be different, and a person skilled in the art can select the metal active components according to the conventional means, and the details are not repeated herein.
According to a preferred embodiment of the present invention, the spent hydrogenation catalyst has a specific surface area of 30 to 300m2The pore volume is 0.05-0.7mL/g, and the most probable pore diameter is more than 1 nm; further preferred isThe specific surface area of the waste hydrogenation catalyst is 30-200m2The pore volume is 0.05-0.5mL/g, and the most probable pore diameter is more than 2 nm; more preferably, the spent hydrogenation catalyst has a specific surface area of from 50 to 150m2The pore volume is 0.1-0.5mL/g, and the most probable pore diameter is 3-8 nm.
In the present invention, specific surface area, pore volume and the most probable pore diameter of the spent hydrogenation catalyst are measured by a low-temperature nitrogen adsorption method, unless otherwise specified.
The inventor of the invention finds that the hydrogenation catalyst obtained by adopting the waste hydrogenation catalyst meeting the physicochemical characteristics to process is preferably used for heavy oil and/or residual oil hydrogenation treatment, and has higher desulfurization and carbon residue removal performance.
The inventors of the present invention have also found that the use of a spent hydrogenation catalyst having a particle size of 10 to 30 mesh, preferably 14 to 20 mesh, and more preferably 16 to 20 mesh, can further improve the desulfurization and carbon residue removal performance of the resulting hydrogenation catalyst. Spent hydrogenation catalyst may be screened prior to use to yield a spent hydrogenation catalyst meeting the preferred particle size requirements described above. Therefore, the method provided by the invention preferably further comprises the step of screening the waste hydrogenation catalyst before the step 1).
According to the invention, in the step 1), the oxygen-containing atmosphere provides oxygen for the charcoal burning and pore expanding treatment of the waste hydrogenation catalyst, and the invention has a wide selection range of the content of the oxygen in the oxygen-containing atmosphere, for example, the volume content of the oxygen in the oxygen-containing atmosphere can be 8-30%, and preferably 10-25%. The oxygen-containing atmosphere according to the present invention can be provided by different methods according to different requirements of the oxygen volume content, for example, the oxygen-containing atmosphere can be provided by air, when the requirement for the oxygen content of the oxygen-containing atmosphere is high, the oxygen-containing atmosphere can be provided by air and oxygen together, and when the requirement for the oxygen content of the oxygen-containing atmosphere is low, the oxygen-containing atmosphere can be provided by air and inert atmosphere (for example, nitrogen) together. The embodiment of the present invention is exemplified by using air to provide the oxygen-containing atmosphere, which is more favorable for cost saving, but the present invention is not limited thereto.
The charring and reaming processes of the present invention may be carried out in conventional equipment, provided that step 1) is carried out in an oxygen-containing atmosphere under optional stage (1) and stage (2) conditions, for example in a muffle furnace.
In the invention, the step 1) can be optionally performed in the stage (1), that is, the step 1) of the invention comprises the stage (1) and the stage (2), or the step 1) of the invention comprises only the stage (2). The conditions of the stage (2) of the step 1) of the invention comprise: the temperature is 500-850 ℃ and the time is 1-10 hours, while in the prior art, the coke-burning treatment of the spent hydrogenation catalyst is generally carried out without and without being above 500 ℃, for example, the coke-burning temperature disclosed in CN1921942A is not more than 500 ℃, preferably 350-425 ℃, and the coke-burning temperature disclosed in CN106669866A is below 480 ℃. The inventor of the invention finds that the spent hydrogenation catalyst is subjected to carbon burning and pore-expanding treatment under the conditions of the temperature of 500-850 ℃ and the time of 1-10 hours, and the hydrogenation catalyst obtained by combining the treatment of the step 2) is particularly suitable for the heavy oil and/or residual oil hydrogenation treatment process. Preferably, the charking and pore-expanding treatment in step 1) of the present invention comprises a stage (1) and a stage (2), and this preferred embodiment is more beneficial to improve the desulfurization and carbon residue removal activity of the obtained hydrogenation catalyst in the heavy oil and/or residual oil hydrotreating process.
According to the invention, preferably, the conditions of said stage (1) comprise: the treatment is carried out at a temperature of 200-300 ℃ for 1-3 hours and then at a temperature of 300-500 ℃ for 1-4 hours.
According to the invention, preferably, the conditions of said phase (2) comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-8 hours;
further preferably, the conditions of stage (1) include: treating at the temperature of 230-280 ℃ for 1-3 hours, and then treating at the temperature of 350-450 ℃ for 1-4 hours; the conditions of the stage (2) include: the temperature is 600 ℃ and 750 ℃ and the time is 1-4 hours. The hydrogenation catalyst obtained by adopting the optimized conditions of carbon burning and hole expanding increases the accessibility of the active center of the catalyst to macromolecular compounds in heavy oil and/or residual oil, improves the diffusion performance of the catalyst pore passage, and can obtain better desulfurization and carbon residue removal effects when the obtained hydrogenation catalyst is used in the heavy oil and/or residual oil hydrogenation treatment process.
The impregnation in step 2) according to the present invention is not particularly limited, and for example, the impregnation may be an equal volume of saturated impregnation, unsaturated impregnation or supersaturated impregnation, that is, step 2) may impregnate the solid product obtained in step 1) with an equal volume of saturated impregnation, unsaturated impregnation or supersaturated impregnation of a solution containing an organic compound. The equal-volume saturated impregnation, unsaturated impregnation or supersaturated impregnation method can be carried out according to the conventional technical means in the field, and the method is not particularly limited in this respect and is not described in detail any more. According to a preferred embodiment of the invention, the impregnation is an isovolumetric saturation impregnation.
In the present invention, the impregnation may be carried out at room temperature (e.g., 20 to 40 ℃) for 1 to 10 hours.
According to the invention, preferably, the weight ratio of the solid product obtained in step 1) to the organic compound is 3 to 200: 1, more preferably 6 to 150: 1, more preferably 6 to 60: 1, more preferably 8 to 10: 1. the preferred ratio is more favorable for achieving more uniform redispersion of the active metal in the solid product. It should be noted that, the weight ratio of the solid product obtained in step 1) to the organic compound and the concentration of the solution containing the organic compound can be determined by those skilled in the art by the impregnation method described above, and for example, when the solid product obtained in step 1) is impregnated with an equal volume of the solution containing the organic compound, the concentration of the solution containing the organic compound can be determined based on the water absorption of the solid product obtained in step 1) and the weight ratio of the solid product obtained in step 1) to the organic compound.
According to the present invention, specifically, the organic alcohol may be at least one of a monohydric alcohol, a dihydric alcohol and a trihydric alcohol, and the present invention is not particularly limited thereto, and preferably, the organic alcohol is ethylene glycol and/or glycerol, and most preferably, the organic alcohol is glycerol; the organic acid may be at least one of a monobasic acid, a dibasic acid and a polybasic acid, preferably, the organic acid includes an aminocarboxylic acid, and further preferably, the organic acid includes at least one of citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid and diethylenetriaminepentaacetic acid. According to a preferred embodiment of the present invention, the organic compound is at least one selected from the group consisting of glycerol, citric acid, ethylenediaminetetraacetic acid, monoethanolamine, diethylenetriamine, hydroxyethylethylenediamine, nitrilotriacetic acid and diethylenetriaminepentaacetic acid, more preferably at least one selected from the group consisting of glycerol, citric acid and ethylenediaminetetraacetic acid, and most preferably glycerol and/or citric acid. The adoption of the preferable organic compound is more beneficial to improving the desulfurization and carbon residue removal performance of the obtained hydrogenation catalyst.
In the present invention, the drying conditions in step 2) are not particularly limited, and for example, the drying conditions include: the temperature is 90-200 ℃ and the time is 2-10 hours, preferably, the temperature is 100-170 ℃ and the time is 2-5 hours.
The second aspect of the invention provides a hydrogenation catalyst obtained by the method for treating the waste hydrogenation catalyst, wherein the specific surface area of the catalyst is 80-250m2The pore volume is 0.2-0.9mL/g, and the most probable pore diameter is 5-14 nm. The hydrogenation catalyst obtained by the treatment method is used in the heavy oil and/or residual oil hydrogenation treatment process, and has high desulfurization and carbon residue removal performances.
Accordingly, a third aspect of the present invention provides the use of a hydrogenation catalyst as described above in the hydroprocessing of heavy oils and/or residues. Specifically, the hydrogenation catalyst is contacted and reacted with heavy oil and/or residual oil under the condition of heavy oil and/or residual oil hydrotreating and in the presence of hydrogen.
The hydrogenation catalyst provided by the invention is suitable for treating various heavy oils and residual oils. In the present invention, "residue" means a component remaining at the bottom of a distillation tower in the distillation of crude oil, including atmospheric residue and vacuum residue. The heavy oil refers to heavy raw oil blended from residual oil and coker gas oil. The crude oil refers to natural petroleum produced from underground, and is a liquid mineral product with hydrocarbon as a main component. The heavy oil and/or oil residue has a high sulfur content and a high carbon residue content, for example, a sulfur content of at least 1 wt% and a carbon residue content of at least 10 wt% in the heavy oil and/or oil residue.
The heavy oil and/or residue hydrotreating conditions of the present invention are not particularly limited, and preferably, the heavy oil and/or residue hydrotreating conditions include: the temperature is 330--1The volume ratio of hydrogen to oil is 500-1200.
The present invention will be described in detail below by way of examples.
In the following examples, the specific surface area, pore volume and most probable pore diameter were measured by a low-temperature nitrogen adsorption method.
The carbon content in the catalyst was determined by a carbon sulfur analyzer.
The carbon residue content (wt%) in the oil product was determined according to the method of GB 17144.
Example 1
1) Taking industrial deactivated diesel hydrogenation catalyst (carbon deposit 6.82 wt%, inactive metal content 1.5 wt%, the catalyst is NiMo/Al2O3Taking the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst as a reference, the content of Ni is 3.4 wt% and the content of Mo is 22 wt% calculated by oxide, namely a deactivator A, sieving the deactivator A to obtain the deactivator A with 16-20 meshes, putting the deactivator A into a muffle furnace, and carrying out charcoal burning and hole expanding treatment in an air atmosphere by a temperature programming mode, wherein the treatment comprises the following steps: the temperature of the stage (1) is kept constant at 250 ℃ for 1 hour, the temperature of the stage (2) is kept constant at 350 ℃ for 2 hours, and then the temperature of the stage (2) is kept constant at 600 ℃, 650 ℃ and 700 ℃ for 2 hours respectively to obtain a regenerant B, C, D;
2) preparing an aqueous solution of citric acid, respectively soaking the regenerant B, C, D in an isometric saturated soaking method, sealing and placing for 3 hours at room temperature (25 ℃), wherein the mass ratio of the regenerant B, C, D to the citric acid is 7.2, and then drying for 3 hours at 140 ℃ in an air atmosphere to obtain hydrogenation catalysts F1, F2 and F3.
Comparative example 1
1) The deactivator A obtained by the screening treatment of the example 1 is put into a muffle furnace, and is subjected to charcoal burning treatment in a temperature programming manner under an air atmosphere, wherein the charcoal burning treatment comprises the following steps: keeping the temperature at 250 ℃ for 1 hour, keeping the temperature at 350 ℃ for 2 hours, and keeping the temperature at 400 ℃ for 2 hours to obtain a regenerant E;
2) the procedure of example 1, step 2) was followed, and the regenerant E was impregnated with an aqueous solution of citric acid saturated with an equal volume, which was left under sealed conditions at room temperature (25 ℃) for 3 hours and then dried at 140 ℃ for 3 hours under an air atmosphere to obtain a hydrogenation catalyst G.
The physical and chemical properties of the deactivator A, the regenerant B, C, D, E, and the hydrogenation catalysts F1, F2, F3, and G described in the above examples and comparative examples are shown in Table 1.
TABLE 1
| Carbon content/weight% | Specific surface area/m2·g-1 | Pore volume/cm3·g-1 | Most probable pore diameter/nm | |
| A | 6.82 | 112.36 | 0.228 | 3.84 |
| B | 0.12 | 128.56 | 0.331 | 8.15 |
| C | 0.10 | 115.72 | 0.345 | 8.90 |
| D | 0.08 | 94.31 | 0.342 | 10.46 |
| E | 0.23 | 176.17 | 0.280 | 5.53 |
| F1 | - | 132.17 | 0.339 | 8.32 |
| F2 | - | 114.54 | 0.350 | 9.08 |
| F3 | - | 91.96 | 0.348 | 10.63 |
| G | - | 182.28 | 0.297 | 5.74 |
Table 1 shows the basic physical and chemical properties of the agents A-G, respectively, the carbon content of the deactivator A is high, the pore channels are filled with carbon deposition, and the pore volume and the most probable pore diameter are smaller. Compared with the deactivator A, the carbon content of the regenerant B, C, D after the charring and pore expanding treatment is reduced, and the pore volume and the most probable pore diameter are obviously increased. In addition, the pore volume and the most probable pore diameter of the regenerant B, C, D subjected to the charring and pore expansion treatment are obviously larger than those of the regenerant E subjected to the conventional charring treatment only at 400 ℃. Compared with the regenerant B, C, D, E, after the hydrogenation catalysts F1-F3 and G are activated by the impregnation liquid containing organic compounds, the aggregated active metals are redispersed, so that the partially blocked pore channels are dredged, and the pore volume and the most probable pore diameter are correspondingly increased. In general, the pore volume and the most probable pore diameter of the hydrogenation catalyst F1-F3 obtained by the treatment method provided by the invention are obviously larger than those of the catalyst G which is subjected to only carbon burning and redispersion treatment.
Example 2
The procedure is as in example 1, except that stage (2) of stage 1) is thermostatted at 550 ℃ for 2 hours to obtain the hydrogenation catalyst H.
Example 3
The procedure is as in example 1, except that stage (2) of stage 1) is thermostatted at 800 ℃ for 2 hours to obtain hydrogenation catalyst I.
Example 4
The procedure of example 1 was followed, except that stage 1) was not conducted and stage 2 was kept at 650 ℃ for 5 hours, to obtain hydrogenation catalyst J.
Example 5
The procedure of example 1 was followed, except that in step 2), stage (2) was kept at 650 ℃ for 2 hours, and in step 1), citric acid was replaced with hydroxyethyl ethylenediamine of equal mass to obtain hydrogenation catalyst K.
Test example 1
This test example was used to measure the residue hydrotreating performance of the above hydrogenation catalyst. The residual oil hydrodesulfurization catalyst (NiMo/Al) developed by the research institute of petrochemical engineering science of China petrochemical Co., Ltd is adopted2O3Ni content of 3.0 wt% and Mo content of 15.4 wt%, calculated as oxide), was used as a reference agent for the evaluation test. Specifically, the hydrogenation catalysts obtained in the above examples and comparative examples were evaluated in a fixed bed reactor for heavy oil hydrogenation using atmospheric residue of crude oil imported from the middle east (properties of which are shown in Table 2) as a feedstock, and desulfurization and carbon residue removal performance of the respective catalysts were compared. The loading amount of the hydrogenation catalyst is 120 mL; evaluation conditions were as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14MPa, and the liquid hourly space velocity is 0.5h-1The volume ratio of hydrogen to oil is 600: 1. The results are shown in Table 3.
The specific calculation method of the desulfurization rate and the carbon residue removal rate is as follows:
TABLE 2
TABLE 3 evaluation results of catalysts
| Desulfurization rate/%) | Percent carbon removal /) | |
| F1 | 86.3 | 57.8 |
| F2 | 87.9 | 58.1 |
| F3 | 83.4 | 55.2 |
| G | 62.9 | 41.8 |
| H | 84.2 | 55.4 |
| I | 81.1 | 54.1 |
| J | 84.3 | 55.9 |
| K | 81.6 | 54.5 |
| Reference agent | 85.5 | 57.3 |
From the results in table 3, it can be seen that the hydrodesulfurization and carbon residue removal activities of the hydrogenation catalyst G are significantly lower than those of the reference agent, while the hydrodesulfurization and carbon residue removal activities of the hydrogenation catalyst obtained by the method provided by the present invention are substantially equivalent to those of the reference agent, while the hydrodesulfurization activities of F1 and F2 are higher than those of the reference agent. The results in table 3 show that the industrial deactivated diesel oil hydrogenation catalyst is applied to the residual oil hydrogenation reaction after the carbon burning and pore expanding treatment combined with the step 2) redispersion treatment by adopting the method provided by the invention, and has better hydrodesulfurization and residual carbon removal effects.
Example 6
1) Taking industrial deactivated wax oil hydrogenation catalyst (carbon deposition 5.51 wt%, inactive metal content 2.8 wt%, the catalyst is NiMo/Al2O3Based on the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst, the content of Ni is 3.7 wt% and the content of Mo is 22.9 wt% calculated by oxide, namely a deactivator A1, the deactivator A1 is sieved to obtain a deactivator A1 with the size of 16-20 meshes, and the deactivator A1 is put into a muffle furnace and subjected to carbon burning and hole expanding treatment in an air atmosphere by means of temperature programming, wherein the method comprises the following steps: stage (1) is constant temperature for 2 hours at 230 ℃, and constant temperature for 2 hours at 380 ℃, and then stage (2) is respectively constant temperature for 2 hours at 600 ℃, 650 ℃ and 700 ℃ to obtain regenerants B1, C1 and D1;
2) preparing an aqueous solution of glycerol, respectively soaking regenerants B1, C1 and D1 by an isometric saturation soaking method, sealing and placing for 3 hours at room temperature (25 ℃), wherein the mass ratio of the regenerants B1, C1 and D1 to the glycerol is 6.9, and then drying for 3 hours at 140 ℃ in an air atmosphere to obtain hydrogenation catalysts L1, L2 and L3.
Comparative example 2
1) The deactivator A1 obtained by the sieving treatment of example 6 was put into a muffle furnace and subjected to a charcoal-burning treatment in a temperature-programmed manner under an air atmosphere, including: keeping the temperature at 230 ℃ for 2 hours, keeping the temperature at 380 ℃ for 2 hours, and then keeping the temperature at 400 ℃ for 2 hours to obtain a regenerant E1;
2) the procedure of example 6, step 2) was followed, and the regenerant E1 was impregnated with an equal volume of an aqueous solution of glycerol under sealed conditions at room temperature (25 ℃ C.) for 3 hours and then dried at 140 ℃ for 3 hours under an air atmosphere to obtain a hydrogenation catalyst G1.
The physical and chemical properties of the deactivator A1, regenerants B1, C1, D1, E1, and hydrogenation catalysts L1, L2, L3, and G1 described in the above examples and comparative examples are shown in Table 4.
TABLE 4
Table 4 shows the basic physical and chemical properties of deactivator A1, regenerants B1, C1, D1 and E1 and hydrogenation catalysts L1, L2, L3 and G1 respectively, the wax oil hydrogenation deactivator A1 has high carbon content, pore channels are filled with carbon deposition, and the pore volume and the most probable pore diameter are smaller. Compared with the deactivator A1, the carbon content of the regenerants B1, C1 and D1 after charring and pore expanding treatment is reduced, and the pore volume and the most probable pore diameter are obviously increased. In addition, the pore volumes and the most probable pore diameters of the regenerants B1, C1 and D1 after the charring and pore expansion treatment are obviously larger than those of the regenerant E1 after the conventional charring treatment at the temperature of 400 ℃. Compared with regenerants B1, C1, D1 and E1, hydrogenation catalysts L1-L3 and G1 are activated by impregnation liquid containing organic compounds, the aggregated active metals are redispersed, the partially blocked pore channels are dredged, and the pore volume and the most probable pore diameter are correspondingly increased. In general, the pore volume and the most probable pore diameter of the hydrogenation catalyst L1-L3 obtained by the treatment method provided by the invention are obviously larger than those of the catalyst G1 which is subjected to only carbon burning and redispersion treatment.
Example 7
The procedure of example 6 was followed, except that in step 2), stage (2) was kept at 650 ℃ for 2 hours, except that in step 1), the mass ratio of the regenerant B1 to glycerol was 4, to obtain a hydrogenation catalyst M.
Example 8
The procedure of example 6 was followed, except that in step 2), stage (2) was kept at 650 ℃ for 2 hours, except that in step 1), the mass ratio of the regenerant B1 to glycerol was 70, to obtain a hydrogenation catalyst N.
Test example 2
The residue hydrotreating performance of the above hydrogenation catalyst was measured by the method of the above test example 1. The results are shown in Table 5.
TABLE 5 catalyst evaluation results
| Desulfurization rate/%) | Percent carbon removal /) | |
| L1 | 85.0 | 56.6 |
| L2 | 86.7 | 57.8 |
| L3 | 82.8 | 55.6 |
| G1 | 61.7 | 40.2 |
| M | 84.6 | 55.9 |
| N | 79.5 | 52.3 |
| Reference agent | 85.5 | 57.3 |
From the results in table 5, it can be seen that the hydrodesulfurization and carbon residue removal activities of the hydrogenation catalyst G1 are significantly lower than those of the reference agent, while the hydrodesulfurization and carbon residue removal activities of the hydrogenation catalyst obtained by the method provided by the present invention are substantially equal to or slightly inferior to those of the reference agent, which can meet the requirements of the residual oil hydrotreating reaction on the catalyst, and the hydrodesulfurization and carbon residue removal activities of L2 are higher than those of the reference agent. The results in table 5 show that the industrial deactivated wax oil hydrogenation catalyst is applied to the residual oil hydrogenation reaction after the combination of carbon burning and pore-expanding treatment and the redispersion treatment in the step 2) by adopting the method provided by the invention, and has better hydrodesulfurization and residual carbon removal effects.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A process for treating a spent hydroprocessing catalyst, the process comprising:
1) under oxygen-containing atmosphere, carrying out charcoal burning and hole expanding treatment on the waste hydrogenation catalyst, wherein the charcoal burning and hole expanding treatment comprises optional stages (1) and (2), and the conditions of the stage (1) comprise: the temperature is 200-500 ℃ and the time is 1-10 hours, and the conditions of the stage (2) comprise: the temperature is 500-850 ℃, and the time is 1-10 hours;
2) impregnating the solid product obtained in the step 1) with a solution containing an organic compound selected from at least one of organic alcohols, organic acids, organic amines and organic ammonium salts of C1-C20, and then drying.
2. The treatment method according to claim 1, wherein the organic compound is at least one of glycerol, citric acid, ethylenediaminetetraacetic acid, monoethanolamine, diethylenetriamine, hydroxyethylethylenediamine, nitrilotriacetic acid, and diethylenetriaminepentaacetic acid, more preferably at least one of glycerol, citric acid, and ethylenediaminetetraacetic acid, and still more preferably glycerol and/or citric acid.
3. The process according to claim 1 or 2, wherein the weight ratio of solid product obtained in step 1) to organic compound is between 3 and 200: 1, more preferably 6 to 60: 1.
4. the process of any one of claims 1 to 3, wherein in step 2), the impregnation is an equal volume saturated impregnation, unsaturated impregnation or supersaturated impregnation.
5. The process of any one of claims 1 to 3, wherein in step 2), the drying conditions comprise: the temperature is 90-200 ℃ and the time is 2-10 hours.
6. The processing method according to any one of claims 1 to 5,
the conditions of the stage (1) include: treating at 200-300 deg.C for 1-3 hr, and then treating at 300-500 deg.C for 1-4 hr;
preferably, the conditions of said stage (2) comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-8 hours;
preferably, the conditions of stage (1) include: treating at the temperature of 230-280 ℃ for 1-3 hours, and then treating at the temperature of 350-450 ℃ for 1-4 hours; the conditions of the stage (2) include: the temperature is 600 ℃ and 750 ℃ and the time is 1-4 hours.
7. The process according to any one of claims 1 to 6, wherein the oxygen-containing atmosphere has a volume content of oxygen of 8 to 30%, preferably 10 to 25%.
8. The process of any one of claims 1 to 7, wherein the spent hydrogenation catalyst comprises at least one of a spent gasoline hydrogenation catalyst, a spent diesel hydrogenation catalyst, a spent kerosene hydrogenation catalyst, and a spent wax oil hydrogenation catalyst;
preferably, the carbon content of the spent hydrogenation catalyst is less than 30 wt% and the inactive metal content is less than 20 wt%, based on the total amount of the spent hydrogenation catalyst, and further preferably, the carbon content of the spent hydrogenation catalyst is less than 15 wt% and the inactive metal content is less than 10 wt%;
preferably, the spent hydrogenation catalyst has a specific surface area of from 30 to 300m2The pore volume is 0.05-0.7mL/g, and the most probable pore diameter is more than 1 nm; further preferably, the specific surface area of the spent hydrogenation catalyst is in the range of 30 to 200m2The pore volume is 0.05-0.5mL/g, and the most probable pore diameter is more than 2 nm; more preferably, the spent hydrogenation catalyst has a specific surface area of from 50 to 150m2The pore volume is 0.1-0.5mL/g, and the most probable pore diameter is 3-8 nm;
preferably, the spent hydrogenation catalyst comprises a carrier and a metal active component supported on the carrier, the metal active component comprising molybdenum and/or tungsten and nickel and/or cobalt; further preferably, the content of molybdenum and/or tungsten is 10-40 wt% and the content of nickel and/or cobalt is 1.5-8 wt% calculated on oxide basis based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst.
9. A hydroprocessing catalyst obtained by a process for the treatment of a spent hydroprocessing catalyst as defined in any one of claims 1-8, said catalyst having a specific surface area of from 80 to 250m2The pore volume is 0.2-0.9mL/g, and the most probable pore diameter is 5-14 nm.
10. Use of the hydrogenation catalyst of claim 9 in the hydroprocessing of heavy oils and/or residues.
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| CN102463127A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Regeneration and activation method for catalyst |
| CN104624248A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | Regeneration activation method of heavy oil and residual oil hydrotreating catalyst |
| US20170036196A1 (en) * | 2014-04-16 | 2017-02-09 | Catalyst Recovery Europe S.A. | Process for rejuvenating hydrotreating catalysts |
| CN105944735A (en) * | 2016-05-26 | 2016-09-21 | 盘锦鑫安源化学工业有限公司 | Activating method of II type hydrogenation catalyst with carbon deposit inactivation |
| CN109174207A (en) * | 2018-07-11 | 2019-01-11 | 上海英保能源化工科技有限公司 | A kind of activity of hydrocatalyst restores and vulcanization process |
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