CN115957827A - Activation regeneration method of fluidized bed residual oil hydrogenation catalyst - Google Patents
Activation regeneration method of fluidized bed residual oil hydrogenation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 230000004913 activation Effects 0.000 title claims abstract description 48
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000011069 regeneration method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000003513 alkali Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 11
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000011343 solid material Substances 0.000 claims abstract description 4
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 238000005470 impregnation Methods 0.000 claims description 22
- 238000007789 sealing Methods 0.000 claims description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 19
- 239000001099 ammonium carbonate Substances 0.000 claims description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 28
- 239000002184 metal Substances 0.000 abstract description 28
- 239000011148 porous material Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 9
- 230000009471 action Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000012535 impurity Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization 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
- 230000008929 regeneration Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 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
- 235000012501 ammonium carbonate Nutrition 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
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 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
- 239000012798 spherical particle Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
Abstract
The invention discloses an activation regeneration method of a boiling bed residual oil hydrogenation catalyst, which comprises the following steps: (1) Carrying out roasting activation pretreatment on the boiling bed residual oil hydrogenation catalyst which is partially deactivated or completely deactivated; (2) Performing alkali activation treatment on the pretreated material in the step (1), performing solid-liquid separation on the treated material, and drying the solid material to obtain an alkali activated material and a filtrate; (3) Carrying out acid activation treatment on the alkali activation material obtained in the step (2), and drying the treated material to obtain an acid activation material; (4) Standing the filtrate obtained in the step (2) at a low temperature, filtering, obtaining solid phase crystals which are ammonium vanadate after filtering, and concentrating the filtrate after filtering to obtain a solution; (5) And (4) dipping the catalyst in the solution obtained in the step (4), drying and roasting to obtain the regenerated catalyst. The invention can effectively improve the pore structure of the deactivated catalyst and the action of the active metal and the carrier, the metal dispersibility of the activated catalyst is good, the waste catalyst is utilized to the maximum extent, and the process is simple and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of catalyst regeneration, and particularly relates to an activation regeneration method of a fluidized bed residual oil hydrogenation catalyst.
Background
With the aggravation of crude oil deterioration trend and the increasingly stricter environmental regulations, the residue hydrogenation technology has become a key technology for improving the yield of light oil in oil refineries. Residua is the heaviest, most structurally complex portion of petroleum fractions that are enriched in most of the impurities in the crude oil, such as sulfur, nitrogen, heterocyclic compounds, soluble metal compounds, gums, asphaltenes, and the like, and thus are the most difficult fractions to process. The fluidized bed hydrogenation technology has the advantages of strong adaptability to raw oil, basically no pressure drop in the reactor, uniform temperature distribution, good mass transfer and heat transfer, online addition and discharge of the catalyst, high utilization rate of the catalyst, long running period, flexible device operation and the like, and is continuously developed in recent years.
In the hydrogenation reaction process, heavy oil and residual oil contain a large amount of metal impurities such as nickel, vanadium, iron and the like, and are easy to deposit in a hydrotreating catalyst in the hydrotreating process, so that the hydrotreating catalyst is inactivated. The main components of the boiling bed residual oil hydrogenation deactivated catalyst are alumina, active metal components (molybdenum oxide and nickel oxide) and deposits of metal impurities such as nickel, vanadium and the like in residual oil (the deposits can exceed more than 20 percent of the weight of the waste catalyst). If the deactivated catalyst is simply buried, it will pollute the environment and waste resources, so the activation of the deactivated catalyst will be appreciated by people.
CN1258754A discloses a method for recovering metals from Co-Mo series waste catalysts. The method comprises the steps of roasting, crushing, dissolving ammonia, filtering the waste catalyst, replacing cobalt in a complex with zinc, and then adding nitric acid to recover MoO 3 The filter residue is dissolved with sulphuric acid and ammonium alum is separated with ammonium sulphate to remove most of the aluminium. CN1752021A discloses a method for producing vanadium pentoxide by using vanadium-containing waste catalyst. The method comprises removing deposited oil in catalyst, pulverizing, oxidizing, and recovering by alkali treatmentSodium vanadate and sodium molybdate. Adding excessive ammonium chloride into the leachate to enable sodium vanadate to generate ammonium metavanadate, and decomposing at 800-850 ℃ to generate molten vanadium pentoxide. CN 112746172A discloses a treatment method of an inactivated hydrogenation catalyst, which comprises carbonization, hydrothermal treatment, alkali treatment and hydrogen reduction treatment. The treatment method can save the step of removing oil from the oil-containing deactivated hydrogenation catalyst in the existing method, greatly reduce the energy consumption of a treatment device, shorten the process flow and effectively recover high-value metal components such as molybdenum, vanadium, nickel, aluminum and the like in the deactivated hydrogenation catalyst. The above method is only to recover the metal therein, and does not realize the activation regeneration of the catalyst.
CN111097440A discloses a regeneration method of a deactivated residual oil hydrotreating catalyst, which comprises the following steps: the method comprises the steps of carrying out charcoal burning and sulfur removal pretreatment on the deactivated residual oil hydrotreating catalyst, then carrying out unsaturated impregnation or saturated impregnation by using an acidic solution containing a complexing agent, carrying out impregnation treatment by using an alkaline solution, carrying out heat treatment in an ammonia-containing atmosphere, drying and roasting to obtain a regenerated hydrotreating catalyst. Although the method can utilize deposited metal impurities to make the deposited metal impurities be used as active metal in the regenerated catalyst and can improve the pore structure of the catalyst, the regeneration process is more complicated and the cost is higher, thus being not beneficial to industrial production.
CN 111826194A discloses a residual oil hydrotreating method, which relates to the method that the hydrodesulfurization catalyst is obtained by treating waste hydrodesulfurization catalyst, and the specific surface area of the hydrodesulfurization catalyst is 50-350m 2 The pore volume is 0.2-1mL/g, and the most probable pore diameter is 5-15nm. The process cannot fully utilize the active components in the original catalyst, and the active components need to be supplemented, so that the regeneration process is complicated, and the industrial production is not facilitated. In addition, in the process of carbon burning of the residual oil hydrogenation catalyst in the existing method, active components are easy to aggregate, and the regenerated catalytic activity is influenced to a great extent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an activation regeneration method of a boiling bed residual oil hydrogenation catalyst, which can effectively improve the pore structure of the deactivated catalyst and the action of active metal and a carrier by carrying out acid-base activation treatment on the deactivated boiling bed hydrogenation catalyst, has good metal dispersibility of the activated catalyst, utilizes the waste catalyst to the maximum extent, and has simple and environment-friendly process.
The method for activating and regenerating the boiling bed residual oil hydrogenation catalyst comprises the following steps:
(1) Carrying out roasting activation pretreatment on the boiling bed residual oil hydrogenation catalyst which is partially inactivated or completely inactivated to obtain a pretreatment material A;
(2) Performing alkali activation treatment on the pretreated material A in the step (1), performing solid-liquid separation on the treated material, and drying the solid material to obtain an alkali activated material B and a filtrate C;
(3) Carrying out acid activation treatment on the alkali activation material B in the step (2), and drying the treated material to obtain an acid activation material D;
(4) Standing the filtrate C obtained in the step (2) at a low temperature, filtering, obtaining solid phase crystals which are ammonium vanadate after filtering, and concentrating the filtrate after filtering to obtain a solution E;
(5) And (4) dipping the acid activated material D by using the solution E obtained in the step (4), and drying and roasting the dipped material to obtain the activated catalyst.
In the method of the present invention, the deactivated or completely deactivated ebullated bed residual oil hydrogenation catalyst in step (1) generally refers to a catalyst which is partially deactivated or does not meet the reaction requirement due to deposition of heavy metals such as vanadium, iron, etc. and carbon deposition in the ebullated bed residual oil hydrotreating process, and the catalyst may be in a strip shape or a spherical shape, preferably a spherical shape; the deactivated catalyst contains V5-25 wt%, mo 3-20 wt%, ni 2-15 wt% and alumina 40-80 wt%.
In the method of the present invention, the calcination activation treatment in step (1) is carried out at a calcination temperature of 500 to 850 ℃, preferably 550 to 750 ℃, for a calcination time of 6 to 12 hours, preferably 8 to 10 hours, depending on the carbon and sulfur contents of the final catalyst, so that the carbon content in the final catalyst is less than 0.5wt% as carbon element and the sulfur content is less than 0.2wt% as sulfur element. The calcination can be carried out in an oxygen-containing atmosphere with an oxygen content of 20v% to 100v%, such as an air atmosphere or an oxygen atmosphere, preferably, the calcination activation is carried out in an oxygen atmosphere.
In the method of the present invention, before the deactivated catalyst is calcined and activated, the deactivated catalyst is preferably washed and extracted by using an organic solvent to wash away residual oil reaction raw materials on the surface and inside the deactivated catalyst.
In the method of the present invention, the alkali activation treatment in the step (2) is a sealing heat treatment in which the pretreatment material a, ammonium bicarbonate and water are mixed. The mass ratio of the ammonium bicarbonate to the pretreatment material A is 4:1-8:1, the mass ratio of the water consumption to the total mass of the ammonium bicarbonate and the pretreatment material A is 1.5; the pretreatment material A, the ammonium bicarbonate and the water can be added and mixed in any sequence, for example, the water is added into the mixture of the pretreatment material A and the ammonium bicarbonate, or the pretreatment material A is immersed into the aqueous solution of the ammonium bicarbonate. The sealing heat treatment is carried out in a sealing device, preferably a high-pressure reaction kettle. The temperature of sealing heat treatment is 120-180 ℃, preferably 130-170 ℃, and the treatment time is 4-10 hours, preferably 4-8 hours.
In the method, the drying temperature in the step (2) is 60-160 ℃, and the drying time is 4-8 hours.
In the method, the acid activation treatment in the step (3) is sealing heat treatment after the material B is activated by using organic acid to soak alkali. The organic acid is one or a mixture of oxalic acid, citric acid, acetic acid and tartaric acid, and oxalic acid is preferred. The organic acid is impregnated by adopting step impregnation, preferably two-step impregnation, wherein the mass percent concentration of the organic acid solution in the first step of impregnation is 10-20%, the solution dosage is 60-80 v% of the saturated water absorption capacity of the alkali activated material B, the mass percent concentration of the organic acid solution in the second step of impregnation is 20-30%, and the solution dosage is 20-40 v% of the saturated water absorption capacity of the alkali activated material B. Spray impregnation is adopted during impregnation. The sealing heat treatment is carried out in a sealing device, preferably a high-pressure reaction kettle. The sealing heat treatment is carried out at a temperature of 30 to 60 deg.C, preferably 40 to 60 deg.C, for 4 to 10 hours, preferably 5 to 8 hours.
In the method, the drying temperature in the step (3) is 60-160 ℃, and the drying time is 4-8 hours.
In the method, the low-temperature standing temperature in the step (4) is 1-10 ℃, the standing time is 12-48h, and crystals are not precipitated in the solution during standing.
In the method of the invention, the concentration in the step (4) is generally concentrated by evaporation until the concentration of molybdenum in the solution is 8-20g/100mL calculated by oxide.
In the method of the present invention, the impregnation in step (5) may be an equal volume impregnation or an over volume impregnation, preferably an equal volume impregnation, and the impregnation time is 1 to 4 hours.
In the method, the drying temperature in the step (5) is 80-160 ℃, the drying time is 6-10 hours, and the roasting is 4-8 hours at the temperature of 450-550 ℃.
Compared with the prior art, the invention has the following advantages: the method of the invention basically does not destroy the strength and shape of the original catalyst and recovers the activity of the catalyst to the maximum extent through the following processes of roasting activation pretreatment, activation treatment, acid activation treatment, metal recovery by impregnation and the like. When the deactivated catalyst is subjected to roasting activation pretreatment, carbon deposition deposited by the catalyst is removed by oxidation, and pore channels blocked by the carbon deposition in the catalyst are recovered, and on the other hand, metal sulfides in the deactivated catalyst are converted into metal oxides; during alkali activation treatment, metal vanadium deposited by reaction in the deactivated catalyst and active metal molybdenum of the catalyst are dissolved in ammonium bicarbonate solution, and the pore channels blocked by the deposition of the metal vanadium in the deactivated catalyst are effectively recovered due to the dissolution of the metal vanadium. After the vanadium is dissolved in the ammonium bicarbonate solution, the vanadium is separated out from the solution in the form of ammonium vanadate when standing at low temperature, and most of valuable metal vanadium in the waste catalyst can be recovered. When the catalyst is subjected to hydrothermal treatment in an ammonium bicarbonate solution, the alumina is subjected to crystallization reaction under the closed and weakly alkaline hydrothermal condition, so that the pore volume and the specific surface area of the catalyst are improved; during acid activation treatment, organic acid reacts with nickel oxide on one hand to dissolve and redisperse nickel in the deactivated catalyst, so that the dispersion degree of the nickel additive is improved, the effect of the additive on an alumina carrier is improved, and the activity of the catalyst is improved. On the other hand, the organic acid reacts with the alumina carrier to dissolve alumina microparticles in the pore channels of the catalyst, so that the pore connectivity is improved, and the content of macropores of the catalyst is increased. When the organic acid is impregnated, the materials are impregnated step by adopting the organic acid with different concentrations, so that the pore canal on the surface of the activated catalyst is more suitable for the residual oil raw material to diffuse into the catalyst. During acid activation treatment, the treatment conditions are mild, and the pore volume and the specific surface area of the catalyst are not reduced while the macroporous content and the pore connectivity of the catalyst are improved; when active metal is impregnated, the used molybdenum is a molybdenum-containing solution in which vanadium is separated out during alkali activation treatment, so that the active metal molybdenum in the deactivated catalyst can be secondarily utilized as an active component, and the production cost of the catalyst can be effectively reduced. In addition, the active metal molybdenum in the deactivated catalyst is loaded in the catalyst after dissolution and reloading, so that the dispersion degree of the active metal molybdenum in the catalyst can be effectively improved, the interaction between the active metal molybdenum and a carrier can be improved, and the catalytic activity of the catalyst is improved.
Detailed Description
The technical solutions and effects of the present invention are further described below with reference to the following examples, but the present invention is not limited to the following examples.
The BET method: application N 2 Physical adsorption-desorption characterization of the pore structures of the carriers of the examples and the comparative examples, the specific operations are as follows: adopting ASAP-2420 type N 2 And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. Taking a small amount of samples, carrying out vacuum treatment for 3-4 hours at 300 ℃, and finally placing the product under the condition of liquid nitrogen low temperature (-200 ℃) to carry out nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter is obtained according to a BJH model.
XRF characterization: analyzing the components of the sample, the target material Rh and the light path atmosphere by using a Japanese ZSX100e type X-ray fluorescence spectrometer: and (4) vacuum conditions.
The sulfur content in the oil is determined by adopting an SH/T0689-2000 standard method.
And the contents of Ni and V in the oil product are determined by adopting a GB/T34099-2017 standard method.
And measuring the nitrogen content in the oil product by adopting an NB/SH/T0704-2010 standard method.
V + Ni removal rate% = (raw material oil metal V + Ni content-product metal V + Ni content)/raw material oil metal V + Ni content x 100%.
Desulfurization rate% = (raw material oil sulfur content-product sulfur content)/raw material oil sulfur content x 100%.
The denitrification rate% = (raw material nitrogen content-product nitrogen content)/raw material nitrogen content x 100%.
Calculating the relative demetallization rate, the relative desulfurization rate and the relative denitrification rate: the demetallization rate, desulfurization rate and denitrification rate of a certain catalyst are measured, the relative demetallization rate, relative desulfurization rate and relative denitrification rate are respectively defined as 100%, and the impurity removal rate of other catalysts/the impurity removal rate of the defined catalyst multiplied by 100% is the relative impurity removal rate.
The deactivated catalyst adopted in the embodiment is the deactivated catalyst of an ebullated bed residual oil hydrogenation industrial device, oil on the surface of the catalyst is removed through extraction, and the catalyst is dried, and the catalyst after treatment comprises the following components: moO 3 ：11.7%，NiO：5.2%，V 2 O 5 ：17.3%，SiO 2 ：0.8%，Al 2 O 3 :57.1%, C:6.3 percent, wherein the percentage is the mass percentage. The catalyst is spherical particles with the particle diameter of 0.3-1.5 mm.
Example 1
(1) Weighing 200 g of deactivated catalyst (subjected to extraction to remove oil on the surface of the catalyst and drying treatment) of the boiling bed residual oil hydrogenation industrial device, and roasting the deactivated catalyst for 8 hours at 600 ℃ in an oxygen atmosphere to obtain a pretreated material A;
(2) 100 g of the pretreatment material A in the step (1) is weighed, 510 g of ammonium bicarbonate and 1550 g of distilled water are added, and the mixture is magnetically stirred for 30 minutes and then transferred into an autoclave to be sealed for 6.5 hours at the temperature of 140 ℃. And (3) carrying out liquid-solid separation on the treated material, and drying the separated solid material at 120 ℃ for 5 hours to obtain an alkali activated material B. Standing the separated solution at 5 ℃ for 36 hours, filtering the solution after standing, obtaining ammonium vanadate as crystals after filtering, and evaporating and concentrating the filtered solution until the concentration of molybdenum oxide is 12.3g/100mL to obtain a concentrated solution E;
(3) 50 g of the alkali-activated material B (saturated water absorption of 0.8 g/g) obtained in the step (2) is weighed and placed in a spray-dip pan, and the impregnated material B is firstly sprayed with 28mL of oxalic acid solution with the mass concentration of 14.5% in a spray-dip mode, and then continuously sprayed with 12mL of oxalic acid solution with the mass concentration of 23.5%. Placing the sprayed material B in a high-pressure kettle, carrying out sealing heat treatment for 7 hours at 40 ℃, and drying the treated material for 5 hours at 120 ℃ to obtain an acid activated material D;
(4) Weighing 50 g of the acid activated material D obtained in the step (3), impregnating the acid activated material D with the concentrated solution E obtained in the step (2) by an isometric impregnation method, drying the impregnated material at 120 ℃ for 8 hours, and roasting the dried material at 450 ℃ for 6 hours to obtain the activated catalyst Cat1, wherein the properties of the catalyst are shown in Table 1.
Example 2
As in example 1, except that the amount of ammonium hydrogencarbonate added in the alkali activation treatment was 620 g, the temperature in the sealing treatment was 150 ℃ and the treatment time was 5.5 hours. During acid activation treatment, the mass concentration of the oxalic acid solution is 25.5% and the dosage of the solution is 26mL during the first step of spraying and dipping, the mass concentration of the oxalic acid solution is 16.5% and the dosage of the solution is 14mL during the second step of spraying and dipping, the treatment temperature is 45 ℃ during sealing and heat treatment, the catalyst is prepared after 6 hours of treatment, and the properties of the catalyst are shown in Table 1.
Example 3
As in example 1, except that the amount of ammonium hydrogencarbonate added in the alkali activation treatment was 430 g, the temperature in the sealing treatment was 175 ℃ and the treatment time was 4.5 hours. During acid activation treatment, the mass concentration of the oxalic acid solution is 12.5% and the dosage of the solution is 24mL during first-step spraying and dipping, the mass concentration of the oxalic acid solution is 28.0% and the dosage of the solution is 16mL during second-step spraying and dipping, the treatment temperature is 35 ℃ during sealing heat treatment, the catalyst is prepared after 8 hours of treatment, and the properties of the catalyst are shown in Table 1.
Example 4
The same procedure as in example 1 was repeated except that the amount of ammonium hydrogencarbonate added in the alkali activation treatment was 740 g, the temperature in the sealing treatment was 125 ℃ and the treatment time was 7.5 hours. During acid activation treatment, the mass concentration of the oxalic acid solution is 18.5% and the dosage of the solution is 30mL during the first step of spraying and dipping, the mass concentration of the oxalic acid solution is 21.5% and the dosage of the solution is 10mL during the second step of spraying and dipping, the treatment temperature is 55 ℃ during sealing and heat treatment, the catalyst is prepared after 5 hours of treatment, and the properties of the catalyst are shown in Table 1.
Comparative example 1
Catalyst Cat-5 was prepared as in example 1 except that the amount of ammonium bicarbonate added was 150 g, and the catalyst properties are shown in Table 1.
Comparative example 2
In the same way as example 1, except that ammonium bicarbonate was changed to the same amount of ammonium carbonate, ammonium vanadate crystals were not precipitated in the alkali solution after the activation was observed, and catalyst Cat-6 was obtained, and the properties of the catalyst are shown in Table 1.
Comparative example 3
Catalyst Cat-7 was prepared as in example 1 except that the temperature was 100 ℃ during the sealing treatment, and the catalyst properties are shown in Table 1.
Comparative example 4
Catalyst Cat-8 was prepared as in example 1 except that the catalyst was not acid-activated and the catalyst properties are shown in Table 1.
TABLE 1 catalyst Properties
Evaluation of catalytic performance:
the catalyst (Cat-1-Cat-8) after activation was evaluated for its catalytic performance by the following method:
the vacuum residuum is used as raw material, and the raw material oil contains metal (Ni + V) 156 microgram/g, sulfur 1.2wt% and nitrogen 0.7wt%. The performance of the activated catalyst is evaluated on a fixed bed residual oil hydrogenation reaction device, and the reaction conditions are as follows: the reaction temperature is 385 ℃, the hydrogen partial pressure is 10MPa, and the liquid hourly space velocity is 0.7 h -1 The volume ratio of hydrogen to oil is 750, the content of each impurity in the produced oil is measured after 500 hours of reaction, the impurity removal rate is calculated, and the evaluation results are shown in table 2.
TABLE 2 comparison of hydrogenation Performance of activated catalysts
As can be seen from the data in Table 2, the catalyst activated by the method of the present invention has higher hydrodemetallization, hydrodesulfurization and hydrodenitrogenation activities compared with the catalyst after comparative activation.
Claims (13)
1. An activation regeneration method of a boiling bed residual oil hydrogenation catalyst is characterized by comprising the following steps: (1) Carrying out roasting activation pretreatment on the boiling bed residual oil hydrogenation catalyst which is partially inactivated or completely inactivated to obtain a pretreatment material A; (2) Performing alkali activation treatment on the pretreated material A in the step (1), performing solid-liquid separation on the treated material, and drying the solid material to obtain an alkali activated material B and a filtrate C; (3) Carrying out acid activation treatment on the alkali activation material B in the step (2), and drying the treated material to obtain an acid activation material D; (4) Standing the filtrate C obtained in the step (2) at a low temperature, filtering, obtaining solid phase crystals which are ammonium vanadate after filtering, and concentrating the filtrate after filtering to obtain a solution E; (5) And (4) dipping the acid activated material D by using the solution E obtained in the step (4), and drying and roasting the dipped material to obtain the regenerated catalyst.
2. The method of claim 1, wherein: in the step (1), based on the weight of the partially or completely deactivated boiling bed residual oil hydrogenation catalyst, the vanadium content is 5-25% by weight calculated on oxide, the molybdenum content is 3-20% by weight calculated on oxide, the nickel content is 2-15% by weight calculated on oxide, and the alumina content is 40-80% by weight calculated on oxide.
3. The method of claim 1, wherein: the roasting temperature of the roasting activation treatment in the step (1) is 500-850 ℃, the roasting time is 6-12 hours, and the carbon content of the final catalyst is lower than 0.5wt% calculated by carbon element, and the sulfur content is lower than 0.2wt% calculated by sulfur element; the roasting is carried out in an oxygen-containing atmosphere, and the oxygen content is 20-100 v%.
4. The method of claim 1, wherein: the alkali activation treatment in the step (2) is sealing heat treatment after mixing the pretreatment material A, ammonium bicarbonate and water; the temperature of the sealing heat treatment is 120-180 ℃, and the treatment time is 4-10 hours.
5. The method of claim 4, wherein: the mass ratio of the ammonium bicarbonate to the pretreatment material A is 4:1-8:1, the mass ratio of the water to the sum of the ammonium bicarbonate and the pretreatment material A is 1.5.
6. The method of claim 1, wherein: the drying temperature in the step (2) is 60-160 ℃, and the drying time is 4-8 hours.
7. The method of claim 1, wherein: the acid activation treatment in the step (3) is sealing heat treatment after the material B is activated by using organic acid to soak alkali; the sealing heat treatment is carried out at a temperature of 30 to 60 deg.C, preferably 40 to 60 deg.C, for 4 to 10 hours, preferably 5 to 8 hours.
8. The method of claim 7, wherein: the organic acid is one or more of oxalic acid, citric acid, acetic acid or tartaric acid.
9. The method of claim 7, wherein: the organic acid is impregnated by two steps, wherein the mass percent concentration of the organic acid solution is 10-20% in the first step of impregnation, the solution amount is 60-80 v% of the saturated water absorption capacity of the alkali activated material B, the mass percent concentration of the organic acid solution is 20-30% in the second step of impregnation, and the solution amount is 20-40 v% of the saturated water absorption capacity of the alkali activated material B.
10. The method of claim 1, wherein: and (4) keeping the low-temperature standing temperature at 1-10 ℃ for 12-48h.
11. The method of claim 1, wherein: and (4) concentrating by evaporation until the concentration of molybdenum in the solution is 8-20g/100mL in terms of oxide.
12. The method of claim 1, wherein: the impregnation in the step (5) is equal-volume impregnation or over-volume impregnation, and the impregnation time is 1-4 hours.
13. The method of claim 7, wherein: the drying temperature in the step (5) is 80-160 ℃, the drying time is 6-10 hours, and the roasting is carried out for 4-8 hours at the temperature of 450-550 ℃.
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