CN113976136A - Preparation method of hydrodemetallization catalyst - Google Patents
Preparation method of hydrodemetallization catalyst Download PDFInfo
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- CN113976136A CN113976136A CN202110607011.6A CN202110607011A CN113976136A CN 113976136 A CN113976136 A CN 113976136A CN 202110607011 A CN202110607011 A CN 202110607011A CN 113976136 A CN113976136 A CN 113976136A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 25
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 17
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 16
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000000295 fuel oil Substances 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 238000004898 kneading Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 239000011343 solid material Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 231100000572 poisoning Toxicity 0.000 claims description 2
- 230000000607 poisoning effect Effects 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- -1 VIB group metals Chemical class 0.000 claims 2
- 239000002699 waste material Substances 0.000 abstract description 24
- 239000011148 porous material Substances 0.000 abstract description 13
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000001125 extrusion Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- 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
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil 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
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (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 discloses a preparation method of a hydrodemetallization catalyst. The method comprises the following steps: (1) crushing a molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium, and then roasting to obtain a material A; (2) mixing the material A, ammonium bicarbonate and water, transferring the mixed material into a pressure-resistant container for hydro-thermal treatment, carrying out solid-liquid separation on the hydro-thermal treated material, drying the solid material to obtain a material B, standing the separated liquid phase for a period of time, filtering, and concentrating the filtrate to obtain a solution C; (3) and uniformly mixing the material B and the pseudo-boehmite, adding the solution C, uniformly mixing, adding a peptizing agent into the mixed material, kneading and molding, drying and roasting a molded product to obtain a carrier, and loading an active component to the hydrodemetallization catalyst. The method can well remove vanadium in the waste catalyst, and prepare the regenerated catalyst with higher pore volume and specific surface by utilizing each component of the waste catalyst, thereby reducing the production cost and environmental pollution.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of a hydrodemetallization catalyst.
Background
With the deterioration and heaviness of crude oil, the efficient conversion of heavy oil and the improvement of the yield of light oil products become an important trend in the development of oil refining technology. The residue fixed bed hydrogenation technology is an effective means for realizing the high-efficiency conversion of heavy oil. By adopting the technical route, the impurities such as metal, sulfur, nitrogen, carbon residue and the like in the residual oil can be effectively removed, high-quality feed is provided for catalytic cracking, and the strict environmental protection regulation requirements are met while the yield of light oil products is increased. During the processing of heavy oil, the metal compounds in the heavy oil are decomposed, and metal impurities are deposited on the inner surface and the outer surface of the catalyst to block the pore channels, so that the catalyst is even poisoned and deactivated.
In the using process of the catalyst, the catalyst becomes waste due to the loss of the original activity, and the waste catalyst rich in metal is not used, so that resources are wasted and the environment is polluted. Recently, environmental regulations have become more stringent for the disposal of spent catalysts. The waste catalyst is treated by several methods, such as landfill treatment, metal recovery, regeneration or recycling, and is used as a raw material to generate other useful products to solve the problem of the waste catalyst.
CN102441440A discloses a method for preparing a hydrotreating catalyst from a spent catalyst. Grinding the waste hydrotreating catalyst, adding alumina, a binder, an acid solution or an alkaline solution and other raw materials into the ground powder, kneading, molding, drying and roasting the molded sample to obtain the new hydrotreating catalyst. Although the method utilizes the waste catalyst to prepare the new hydrotreating catalyst, the pore volume of the catalyst needs to be further improved.
CN106669847B discloses a method for preparing an alumina carrier, which comprises the following steps: (1) extracting, roasting and screening the deactivated hydrogenation demetalization catalyst; (2) carrying out saturated dipping treatment on the catalyst screened in the step (1) by using an organic acid solution, and filtering and drying after dipping; (3) and (3) carrying out saturated dipping treatment on the deactivated hydrodemetallization catalyst dried in the step (2) by adopting an alkali solution, and then filtering, drying and roasting. (4) And (3) carrying out saturated dipping treatment on the deactivated hydrodemetallization catalyst roasted in the step (3) by using an alkali solution, and then filtering, drying and roasting to obtain the demetallization catalyst carrier. The preparation process of the method is complex, and in addition, the specific surface area and the pore volume of the alumina carrier are required to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a hydrodemetallization catalyst. The method can well remove vanadium in the waste catalyst, and prepare the regenerated catalyst with higher pore volume and specific surface by utilizing each component of the waste catalyst, thereby reducing the production cost and environmental pollution.
The preparation method of the hydrodemetallization catalyst comprises the following steps:
(1) crushing a molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium to a certain particle size, and then roasting to obtain a material A;
(2) mixing the material A, ammonium bicarbonate and water, transferring the mixed material into a pressure-resistant container for hydro-thermal treatment, carrying out solid-liquid separation on the hydro-thermal treated material, drying the solid material to obtain a material B, standing the separated liquid phase for a period of time, filtering, and concentrating the filtrate to obtain a solution C;
(3) uniformly mixing the material B and the pseudo-boehmite, then adding the solution C, uniformly mixing, adding a peptizing agent into the mixed material, kneading and molding, and drying and roasting the molded product to obtain a carrier;
(4) and (3) impregnating the carrier in the step (3) with a hydrogenation active component impregnating solution, and drying and roasting the material to obtain the hydrodemetallization catalyst.
In the method, the molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium in the step (1) generally refers to a catalyst which is inactivated or can not meet the reaction requirement due to deposition of heavy metals such as vanadium, iron and the like and carbon deposit in the hydrogenation treatment processes such as hydrodemetallization, hydrodesulfurization, denitrification and the like of wax oil and residual oil; based on the weight of the catalyst, the content of vanadium is 5-30 percent by oxide, the active component of the catalyst is 3-20 percent by oxide, and the content of nickel is 2-15 percent by oxide.
In the method of the present invention, the molybdenum-nickel heavy oil subjected to vanadium poisoning in step (1) is subjected to hydro-pulverization until the mesh number is more than 80 meshes, preferably more than 200 meshes, and more preferably more than 400 meshes and 800 meshes. The roasting temperature is 700-950 ℃, and the roasting time is 6-12 hours.
In the method, the mass ratio of the ammonium bicarbonate in the step (2) to the material A is 4:1-8:1, and the mass ratio of the water to the sum of the ammonium bicarbonate and the material A is 1.5:1-3:1, preferably 2:1-3: 1; the material A, the ammonium bicarbonate and the water can be added and mixed in any order, the mixing temperature is generally room temperature, the temperature can be properly increased in order to further facilitate the dissolution of the ammonium bicarbonate in the water, but the operation is not necessary.
In the method of the present invention, the hydrothermal treatment conditions in step (2) are as follows: the temperature is 120-160 ℃, and the treatment time is 4-8 hours. The pressure-resistant container is generally a high-pressure reaction kettle.
In the method of the present invention, the solid-liquid separation method in step (2) may be filtration, centrifugation or the like.
In the method of the present invention, the standing in step (2) may be carried out at room temperature, generally not lower than 0 ℃, not higher than 30 ℃, preferably at a standing temperature of 1 to 10 ℃, for a period of time suitable for avoiding an increase in the weight of the crystals precipitated from the solution, generally 72 to 168 hours.
In the method of the invention, the concentration in the step (2) is generally concentrated by evaporation until the concentration of molybdenum in the solution is 0.5-5g/100mL calculated by oxide.
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 mass ratio of the material B in the step (3) to the pseudo-boehmite is 1:10-3: 10.
In the method, the mass ratio of the solution C in the step (3) to the pseudo-boehmite is 3:10-5: 10.
In the method, the kneading molding in the step (3) is carried out by adopting a conventional method in the field, and an extrusion aid can be added according to needs in the molding process, wherein the extrusion aid is sesbania powder. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid or oxalic acid, and the concentration of the peptizing agent is 0.1wt% -3 wt%.
In the method, the drying temperature in the step (3) is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.
In the method, the impregnation liquid of the hydrogenation active metal component in the step (4) is a solution containing VIB group and/or VIII group metals, the VIB group metal is selected from one or more of W, Mo, the VIII group metal is selected from one or more of Co and Ni, the content of the VIB group metal is 5-15g/100mL calculated by metal oxides, the content of the VIII group metal is 2.0-4.5g/100mL calculated by metal oxides, and equal-volume impregnation or supersaturated impregnation can be adopted during impregnation. The drying temperature is 80-160 ℃, the drying time is 6-10 hours, the roasting temperature is 450-550 ℃, and the roasting time is 4-8 hours.
Compared with the prior art, the invention has the following advantages:
(1) the method takes the waste catalyst poisoned by vanadium as a raw material, effectively removes the metal vanadium and molybdenum deposited on the surface of the waste catalyst and in the pore channel through simple hydrothermal treatment, and greatly improves the specific surface area of the treated waste catalyst.
(2) When the waste catalyst is subjected to hydrothermal treatment in an ammonium bicarbonate solution, alumina is subjected to crystallization reaction under the closed and alkalescent hydrothermal condition, so that crystal grains grow up, and when the waste catalyst is mixed and kneaded with pseudo-boehmite for molding, the pore volume and the macropore content of the final alumina carrier are improved due to the existence of large crystal grains.
(3) The metal elements molybdenum and vanadium exist in the filtrate after the waste catalyst is subjected to hydrothermal treatment, the filtrate is subjected to standing and filtering to effectively remove the vanadium, and the residual metal molybdenum is added when the alumina carrier is kneaded and molded, so that the active metal molybdenum in the waste catalyst is secondarily utilized.
(4) The method is simple, and the waste catalyst after partial activation is used for replacing the alumina raw material, thereby changing waste into valuable, reducing the production cost and reducing the environmental pollution.
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. Wt% in the present invention represents a mass fraction.
The BET method: application N2Physical 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 N2And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to 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 below 30nm is obtained according to a BJH model.
Mercury pressing method: the pore diameter distribution of the carriers of the examples and the comparative examples is characterized by applying a mercury porosimeter, and the specific operation is as follows: and characterizing the distribution of sample holes by using an American microphone AutoPore9500 full-automatic mercury porosimeter. The samples were dried, weighed into an dilatometer, degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and filled with mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm-1The distribution ratio of the pore diameter of 100nm or more is measured by mercury intrusion method.
XRF characterization: the components of the sample, the target material Rh, the light path atmosphere were analyzed by using a Japanese ZSX100e X-ray fluorescence spectrometer: and (4) vacuum conditions.
The method adopts NB/SH/T0704-.
The sulfur content in the oil product is determined by adopting an SH/T0689-.
The content of carbon residue in the oil product is determined by adopting an SH/T0266-92 standard method.
And the contents of Ni and V in the oil product are determined by adopting a GB/T34099-2017 standard method.
The V + Ni removal rate is calculated according to the following formula:
percent V + Ni removal rate = (raw material oil metal V + Ni content-product metal V + Ni content)/raw material oil metal V + Ni content is multiplied by 100 percent
The waste catalyst used in the examples is the waste catalyst (containing MoO) of fixed bed residue oil hydrogenation industrial device3：6.3wt%，NiO：10.2 wt %，V2O5：23.4 wt %，Fe2O3：0.4 wt %，Al2O3: 47.3 wt%, C: 11.3 wt%), extracted to remove oil on the surface of the catalyst and dried.
Example 1
(1) Taking the waste catalyst crushed to be more than 500 meshes, and roasting for 8 hours at 850 ℃;
(2) weighing 100 g of the waste catalyst and 550 g of ammonium bicarbonate, adding 1600 g of distilled water into the waste catalyst, stirring the mixture for 20 minutes, transferring the mixed material into a high-pressure kettle, and carrying out sealed heat treatment on the mixed material, wherein the heat treatment conditions are as follows: heating at 145 ℃ for 5.5 hours, filtering the material after hydrothermal treatment, drying a filter cake at 110 ℃ for 6 hours, standing the filtrate at 5 ℃ for 144 hours to precipitate crystals, then filtering, determining that the precipitated crystals are ammonium vanadate, determining that the filtrate is a molybdenum-containing solution, concentrating the solution to 200mL, and determining that the molybdenum content is 2.9g/100mL calculated by oxide;
(3) weighing 100 g of pseudo-boehmite (produced by Shandong aluminum industry Co., Ltd.), 15g of dry filter cake in the step (2) and 1.5 g of sesbania powder, uniformly mixing the materials, then adding 35mL of concentrated solution obtained by standing and filtering in the step (2), continuously mixing, adding a proper amount of aqueous solution dissolved with 3g of acetic acid, kneading, extruding into strips, drying the formed product at 140 ℃ for 6 hours, and roasting at 700 ℃ in air for 5 hours to obtain a carrier;
(4) weighing 30 g of the alumina carrier, placing the alumina carrier in a spray-dip rolling pot, spray-dipping the alumina carrier by using Mo-Ni-P solution with the molybdenum oxide concentration of 6.3g/100mL and the nickel oxide concentration of 2.3g/100mL in a saturated dipping mode, drying the dipped catalyst at 120 ℃, and roasting at 450 ℃ for 5 hours to obtain the catalyst Cat-1, wherein the properties of the catalyst are shown in Table 1.
Example 2
In the same manner as in example 1 except that the calcination temperature of the spent catalyst was 950 ℃, the amount of ammonium hydrogencarbonate added was 650 g, the hydrothermal treatment temperature was 135 ℃, the treatment time was 4.5 hours, the amount of the dried cake added was 20 g, and the amount of the concentrated solution added was 40mL, catalyst Cat-2 was obtained, and the catalyst properties are shown in Table 1.
Example 3
In the same manner as in example 1 except that the calcination temperature of the spent catalyst was 750 ℃, the amount of ammonium hydrogencarbonate added was 450 g, the hydrothermal treatment temperature was 150 ℃, the treatment time was 6.5 hours, the amount of the dried cake added was 10 g, and the amount of the concentrated solution added was 30mL, catalyst Cat-3 was obtained, and the catalyst properties are shown in Table 1.
Example 4
In the same manner as in example 1 except that the calcination temperature of the spent catalyst was 750 ℃, the amount of ammonium hydrogencarbonate added was 450 g, the hydrothermal treatment temperature was 150 ℃, the treatment time was 6.5 hours, the amount of the dried cake added was 10 g, and the amount of the concentrated solution added was 45mL, catalyst Cat-4 was obtained, and the catalyst properties are shown in Table 1.
Comparative example 1
In the same manner as in example 1 except that the amount of ammonium hydrogencarbonate added was 200 g, no ammonium molybdate crystals were precipitated from the filtrate, and the molybdenum concentration of the concentrated solution was 0.31g/100mL in terms of oxide, to obtain comparative catalyst Cat-5, the catalyst properties of which are shown in Table 1.
Comparative example 2
In the same manner as in example 1 except that the amount of ammonium carbonate was changed to the same amount of ammonium bicarbonate, ammonium molybdate crystals were precipitated from the filtrate, and the molybdenum concentration of the solution after concentration was 2.3g/100mL in terms of oxide, to obtain comparative catalyst Cat-6, the catalyst properties of which are shown in Table 1.
Comparative example 3
Comparative catalyst Cat-7 was prepared as in example 1 except that no filtrate was added during the alumina formation and the catalyst properties are shown in Table 1.
Comparative example 4
In the same manner as in example 1, except for this example, in comparison with the commercially available fresh catalyst, the catalyst was Cat-8, and the catalyst properties are shown in Table 1.
TABLE 1 catalyst Properties
Evaluation of catalytic performance:
the catalytic performance of the hydrodemetallization catalyst (Cat-1-Cat-8) prepared in the above way is evaluated, and the evaluation method is as follows:
the vacuum residue listed in table 2 was used as a raw material, and evaluated on a small fixed bed residue hydrogenation reactor, the catalyst was a strip of 2-3 mm in length, and the reaction conditions were as follows: the reaction temperature is 387 ℃, the hydrogen partial pressure is 15.7MPa, and the liquid hourly space velocity is 1.0 hour-1The volume ratio of hydrogen to oil is 758, the content of each impurity in the produced oil is measured after 1500 hours of reaction, the impurity removal rate is calculated, and the evaluation result is shown in table 3.
TABLE 2 Properties of the feed oils
TABLE 3 comparison of catalyst hydrogenation performance
Claims (14)
1. A preparation method of a hydrodemetallization catalyst is characterized by comprising the following steps: (1) crushing a molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium to a certain particle size, and then roasting to obtain a material A; (2) mixing the material A, ammonium bicarbonate and water, transferring the mixed material into a pressure-resistant container for hydro-thermal treatment, carrying out solid-liquid separation on the hydro-thermal treated material, drying the solid material to obtain a material B, standing the separated liquid phase for a period of time, filtering, and concentrating the filtrate to obtain a solution C; (3) uniformly mixing the material B and the pseudo-boehmite, then adding the solution C, uniformly mixing, adding a peptizing agent into the mixed material, kneading and molding, and drying and roasting the molded product to obtain a carrier; (4) and (3) impregnating the carrier in the step (3) with a hydrogenation active component impregnating solution, and drying and roasting the material to obtain the hydrodemetallization catalyst.
2. The method of claim 1, wherein: the molybdenum-nickel heavy oil hydrogenation catalyst poisoned by vanadium in the step (1) has the vanadium content of 5-30 percent by weight calculated by oxide, the active component molybdenum of the catalyst is 3-20 percent by weight calculated by oxide, and the nickel content is 2-15 percent by weight calculated by oxide.
3. The method of claim 1, wherein: the molybdenum-nickel heavy oil subjected to vanadium poisoning in the step (1) is subjected to hydro-pulverization until the mesh number is more than 80 meshes, preferably more than 200 meshes, and more preferably 400-800 meshes.
4. The method of claim 1, wherein: the roasting temperature in the step (1) is 700-950 ℃, and the roasting time is 6-12 hours.
5. The method of claim 1, wherein: the mass ratio of the ammonium bicarbonate in the step (2) to the material A is 4:1-8: 1.
6. The method of claim 1, wherein: the mass ratio of the water to the sum of the ammonium bicarbonate and the material A in the step (2) is 1.5:1-3: 1.
7. The method of claim 1, wherein: the hydrothermal treatment conditions in the step (2) are as follows: the temperature is 120-160 ℃, and the treatment time is 4-8 hours.
8. The method of claim 1, wherein: the standing temperature in the step (2) is not lower than 0 ℃ and not higher than 30 ℃, the standing time is preferably no longer increased by the weight of the crystal precipitated from the solution, and is generally 72 to 168 hours.
9. The method of claim 1, wherein: and (3) concentrating the solution obtained in the step (2) until the concentration of molybdenum in the solution is 0.5-5g/100mL calculated by oxide.
10. The method of claim 1, wherein: the drying temperature in the step (2) is 60-160 ℃, and the drying time is 4-8 hours.
11. The method of claim 1, wherein: the mass ratio of the material B in the step (3) to the pseudo-boehmite is 1:10-3: 10.
12. The method of claim 1, wherein: the mass ratio of the solution C in the step (3) to the pseudo-boehmite is 3:10-5: 10.
13. The method of claim 1, wherein: the drying temperature in the step (3) is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours.
14. The method of claim 1, wherein: the impregnation liquid of the hydrogenation active metal component in the step (4) is a solution containing VIB group and/or VIII group metals, wherein the VIB group metals are selected from one or more of W, Mo, the VIII group metals are selected from one or more of Co and Ni, the content of the VIB group metals is 5-15g/100mL calculated by metal oxides, the content of the VIII group metals is 2.0-4.5g/100mL calculated by metal oxides, and equal-volume impregnation or supersaturated impregnation is adopted during impregnation.
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| CN101280369A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for recovering high-purity molybdenum from molybdenum-containing dead catalyst |
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Effective date of registration: 20231214 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |