CN110841651A - Boron-containing residual oil hydrotreating catalyst and preparation method thereof - Google Patents
Boron-containing residual oil hydrotreating catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 167
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 14
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 229910017313 Mo—Co Inorganic materials 0.000 claims description 3
- 229910017318 Mo—Ni Inorganic materials 0.000 claims description 3
- 229910008947 W—Co Inorganic materials 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 43
- 239000002184 metal Substances 0.000 abstract description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 36
- 238000006477 desulfuration reaction Methods 0.000 abstract description 11
- 230000023556 desulfurization Effects 0.000 abstract description 11
- 230000002349 favourable effect Effects 0.000 abstract description 10
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 150000002816 nickel compounds Chemical class 0.000 abstract description 8
- 230000003993 interaction Effects 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 4
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 41
- 230000000694 effects Effects 0.000 description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 9
- KRJBVTKYLBPUJC-UHFFFAOYSA-N [B+3].[O-2].[Al+3].[O-2].[O-2] Chemical compound [B+3].[O-2].[Al+3].[O-2].[O-2] KRJBVTKYLBPUJC-UHFFFAOYSA-N 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical group 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- -1 vanadium metal compound Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910003158 γ-Al2O3 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
- B01J23/002—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
- 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
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a boron-containing residual oil hydrotreating catalyst and a preparation method thereof, wherein the catalyst is provided with mesopores which are intensively distributed and have uniform size, the aperture range of the mesopores is 10-30 nm, the in-situ modification of the boron-containing compound is carried out in the pore canal forming process, the surface of the pore canal has strong acidity which is uniformly distributed, the mesopore canal is favorable for the diffusion of macromolecules such as the residue oil and the like, the increase of the acidity of the mesopores of the catalyst is favorable for improving the adsorption and reaction performance of the metal nickel compound and the sulfur compound in the residue oil, the existence of boron weakens the interaction between the active metal of the catalyst and the carrier, is favorable for the formation of the metal hydrogenation active phase, improves the hydrogenation performance of the active metal of the catalyst, is more favorable for, further improving the nickel removal and desulfurization performance of the catalyst, and improving the overall efficacy of the fixed bed residual oil hydrotreating graded catalyst by being used as a transition agent of a demetallization catalyst and a desulfurization catalyst.
Description
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a boron-containing residual oil hydrotreating catalyst and a preparation method thereof, belonging to the field of petrochemical industry.
Background
The vacuum residue has the characteristics of high content of metal compounds, sulfides and nitrides, complex macromolecular structures such as colloid and asphaltene and the like, and difficult processing, and becomes the key point and the difficulty of refinery processing. The fixed bed residual oil hydrotreating technology is an effective means for realizing clean utilization of vacuum residual oil. However, due to the presence of heteroatoms in the residual oil, the hydrotreating catalyst is easily deactivated by the deposition of metals and carbon deposit, the service life of the residual oil hydrotreating catalyst is generally about one year or even shorter, and the use cost of the catalyst is higher. The development of a high-performance residual oil hydrotreating catalyst becomes the key for improving the benefit of the fixed bed residual oil hydrogenation technology.
The residue hydrogenation technology generally adopts a grading technology, and the commonly used catalyst grading comprises the matching of four catalysts. The first stage is protecting agent for removing Fe, Ca, Na and other impurities from residual oil. The catalyst features high porosity of carrier and low content of active metal. The second stage is demetalization catalyst used for removing impurities such as metallic nickel and metallic vanadium in residual oil. The carrier of the catalyst is a macroporous carrier with bimodal pore canal distribution, and active metal is loaded by 5-12%. The third stage is a desulfurization catalyst, the aperture of the carrier is smaller, the acidity is stronger than that of the metal catalyst carrier, and the metal loading reaches 8-15%. The fourth section is mainly a denitrification catalyst used for hydrodenitrification, the acidity is strongest, and the metal loading capacity reaches 12% -25%.
The development of a high-activity and high-stability residual oil hydrotreating catalyst, especially a demetallization catalyst which is easy to deactivate, requires deep research on diffusion, reaction and deposition rules of heavy oil hydrodemetallization, including diffusion and reaction mechanisms of different metal compounds, and matching of different properties of different metal compound removal and catalysts. At present, the development of general hydrodemetallization catalysts is mostly developed around the basis of enlarging the pore diameter of a carrier, namely, in the preparation process of the carrier, a pore-expanding agent and other means are added to obtain a macroporous alumina carrier. Researches show that the demetallization catalyst needs larger pore volume and pore diameter to ensure the metal holding capacity of the catalyst, so that the service life of the catalyst is prolonged, and the running period of the device is prolonged. On the other hand, the macropores of the catalyst can provide suitable diffusion channels for macromolecular reaction materials, so that macromolecular substances can reach the inner surface of the catalyst more easily, the diffusion effect of macromolecular reactants is effectively improved, the deposition of metal in the catalyst can be promoted, and the utilization rate of the catalyst is improved. However, more precise research shows that the bimodal pore catalyst with 10-30 nm mesopores and more than 100nm macropores has higher hydrodevanadinization activity, while the nickel removal activity is relatively low. The main reason is that the vanadium metal compound is polar molecule, which is associated with colloid and asphaltene, and the molecular size is large, large pore channel is needed for diffusion, and weak pore channel acidity can participate in the reaction for removal. The nickel metal compound has weaker polarity, lower association effect with colloid and asphaltene and smaller molecular size, so the required catalyst has smaller pore canal size and can be better removed only by requiring stronger pore canal acidity.
Along with the improvement of the content of metallic nickel and vanadium in the inferior residual oil, in order to better improve the nickel removal activity of the demetallization catalyst, the nickel removal catalyst with more excellent performance needs to be developed in a targeted manner, and simultaneously has certain desulfurization performance as a transition catalyst between the demetallization catalyst and the desulfurization catalyst, so that the use effect of the residual oil hydrotreating technology can be improved more favorably. More accurate research results show that catalyst pore passages required by hydrogenation and nickel removal are more concentrated at 10-30 nm, and the catalyst has higher acidity or higher active metal hydrogenation performance, hydrogenation stability and carbon deposit resistance, so that the adsorption and reaction of the metal nickel compound are facilitated. The former way of modifying the porous acid is mainly realized by adopting a method of impregnating a modifier with a carrier. The carrier prepared by the method is easy to have the phenomena of uneven surface acidity distribution and pore channel blockage, is not beneficial to the dispersion of active metal of the catalyst, and has lower hydrogenation performance, poor carbon deposition resistance and poor stability.
In summary, based on the difference between the diffusion of the compounds such as Ni and V in the residual oil in the catalyst and the reaction characteristics, the hydrodevanadizing activity of the macroporous residual oil hydrodemetallization catalyst is high and the hydrodenickeling activity is low, and it is necessary to develop a hydrodenickeling catalyst more suitable for removing metallic nickel. The catalyst simultaneously has the advantages of concentrated and uniform mesoporous pore channels, and the surface of the pore channels has uniformly distributed strong acidity or higher active metal hydrogenation performance, hydrogenation stability and carbon deposit resistance, so that the nickel removal activity of the catalyst is improved, the desulfurization activity is realized, and the metal removal activity of the graded catalyst is further improved.
Disclosure of Invention
The invention aims to provide a boron-containing residual oil hydrotreating catalyst and a preparation method thereof, aiming at the defects of the prior art, the catalyst is a nickel-removing catalyst in a hydrodemetallization catalyst, a boron-containing compound is added during preparation, uniform boron-aluminum oxide can be formed in the process of forming carrier pore channels to carry out in-situ acid modification, the boron-aluminum oxide can adjust the amount of B acid and L acid on the surface of an alumina carrier, the interaction between active metal of the catalyst and the carrier is mainly weakened, the hydrogenation performance of the active metal of the catalyst is improved, and the hydrogenation removal of the metal nickel compound is more facilitated.
The technical scheme of the application mainly comprises: firstly, adding a proper amount of organic pore-expanding agent in the process of preparing a uniform alumina carrier by adopting a PH swing method to prepare the uniform carrier with the mesoporous aperture of 10-30 nm in centralized distribution; secondly, a boron-containing compound is added into the organic pore-expanding agent solution in the process of preparing the carrier by adopting a PH swing method, so that uniform boron-aluminum oxide can be formed in the process of forming a carrier pore channel, the boron-aluminum oxide can adjust the amount of B acid and L acid on the surface of the alumina carrier, the interaction between the active metal of the catalyst and the carrier is mainly weakened, the hydrogenation performance of the active metal of the catalyst is mainly improved, and the prepared residual oil hydrodemetallization catalyst is more beneficial to hydrogenation reaction and removal of a metal nickel compound.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a boron-containing residuum hydroprocessing catalyst characterized by: the catalyst is concentrated and uniform in pore size of 10-30 nm, meanwhile, in-situ boron-containing compound modification is carried out in the pore channel forming process, and strong-acid alumina which is uniformly distributed on the surface of a pore channel is used as a carrier. More active metals of VIII group and VIB group catalysts are loaded on the mesoporous surface by a specific metal loading method, the pore volume of the catalyst carrier is 0.6-1.2 ml/g, and the specific surface area is 180-350 m2The pore volume of 10-30 nm mesopores accounts for 60-95% of the total pore volume of the carrier, and the prepared catalyst contains MoO3Or WO36.0 to 14.0 w%, preferably 6.5 to 12.0 w%, CoO or NiO 1.0 to 5.0 w%, preferably 1.5 to 3.5 w% (in terms of oxide content), B2O3The content of (A) is 0.05-5.0 w%.
Preferably, the specific surface area of any boron-containing residual oil hydrotreating catalyst carrier is 200-330 m2/g。
Preferably, the pore volume of any one of the boron-containing residual oil hydrotreating catalyst carriers is 0.70-1.0 ml/g.
Preferably, the pore volume of 10-30 nm mesopores of any boron-containing residual oil hydrotreating catalyst carrier accounts for 70-95% of the total pore volume of the carrier.
The hydrodemetallization catalyst prepared by the method can be used for the hydrodemetallization process of various heavy distillate oils and residual oils, and is particularly suitable for the hydrodemetallization process of deasphalted oils and residual oils.
The preparation process of the catalyst provided by the invention is as follows:
(1) preparing a carrier: preparing an aluminum salt solution, mixing sol by adopting a PH swing method, adding an organic pore-enlarging agent solution containing a certain amount of boron-containing compound in the mixing process, introducing the organic pore-enlarging agent solution into a gel forming tank, forming gel at the temperature of 60-90 ℃, and aging, drying, forming and roasting after the gel forming is finished to obtain the alumina carrier; wherein the pH swing range is 4-10, and the pH value of the final reaction system is 8-10;
(2) the alumina carrier obtained in the step (1) is soaked with a certain amount of Mo/W and Co/Ni solution (MoO) in equal volume3/WO3The total mass of the catalyst is 5.0-14.0% of the mass of the catalyst, the total mass of the NiO/CoO is 1.0-5.0% of the mass of the catalyst), and then the catalyst is dried for 2-8 hours at the temperature of 90-150 ℃, and then is roasted for 1-5 hours at the temperature of 600-800 ℃ to obtain the hydrodemetallization catalyst.
Wherein the organic pore-expanding agent in the step (1) is one or more of polystyrene spheres or polymethyl methacrylate spheres, and the diameter of the organic pore-expanding agent is 30-300 nm.
The amount of the polystyrene spheres or the polymethyl methacrylate spheres in the step (1) is 10-20% based on the calcined alumina.
The boron-containing compound in the step (1) is one or more of boric acid, sodium borate and ammonium borate.
The roasting temperature of the carrier in the step (1) is 550-1100 ℃.
The impregnation liquid in the step (2) is one of Mo-Ni, Mo-Co, W-Co and W-Ni mixed solution.
Has the advantages that: the boron-containing compound is added into the organic pore-expanding agent solution in the process of preparing the carrier by adopting a PH swing method, so that uniform boron-aluminum oxide can be formed in the process of forming a carrier pore channel, the boron-aluminum oxide can adjust the amount of B acid and L acid on the surface of an alumina carrier, the interaction between active metal of the catalyst and the carrier is mainly weakened, and the hydrogenation performance of the active metal of the catalyst is mainly improved, so that the prepared residual oil hydrodemetallization catalyst is more beneficial to hydrogenation reaction and removal of a metal nickel compound; the mesoporous aperture of the catalyst is intensively distributed and uniform at 10-30 nm, meanwhile, the in-situ modification is carried out in the pore channel forming process, the surface of the pore channel has strong acidity which is uniformly distributed, the mesoporous pore channel is favorable for the diffusion of macromolecules such as residual oil, the existence of boron weakens the interaction between the active metal of the catalyst and a carrier, is more favorable for the formation of a metal hydrogenation active phase, improves the hydrogenation performance of the active metal of the catalyst, is more favorable for the hydrogenation removal of a metal nickel compound, and the enhancement of the mesoporous acidity of the catalyst is favorable for improving the adsorption and reaction performance of the metal nickel compound and a sulfur compound in the residual oil, so that the nickel and sulfur removal performance of the catalyst is improved, the catalyst can be used as a transition agent of a demetallization catalyst and a desulfurization catalyst, and further improves the overall effect of a fixed bed residual oil, The hydrogenation treatment process of vacuum distillate oil and deasphalted oil.
Detailed Description
The present invention will be further illustrated by way of specific examples, but the present invention is not limited to the following examples.
The invention aims to provide a preparation method of a boron-containing residual oil hydrotreating catalyst aiming at the defects of the prior art. The catalyst is a nickel-removing catalyst in a hydrogenation demetallization catalyst, the catalyst has the advantages that the mesoporous aperture is concentrated and uniform in 10-30 nm, meanwhile, in-situ boron modification is carried out in the pore channel forming process, the pore channel surface has the characteristic of uniformly distributed acidity, the interaction between active metal of the catalyst and a carrier is weakened due to the presence of boron, the formation of a metal hydrogenation active phase is facilitated, the hydrogenation performance of the active metal of the catalyst is improved, and the hydrogenation removal of a metal nickel compound is facilitated. Meanwhile, the catalyst has high nickel removal activity and good desulfurization activity, can be used as a transition agent of a demetallization catalyst and a desulfurization catalyst, and is favorable for improving the overall effect of the fixed bed residual oil hydrogenation graded catalyst.
A boron-containing residual oil hydrotreating catalyst is provided with mesopores, wherein the mesopores are intensively distributed and have uniform size, the pore diameter range of the mesopores is 10-30 nm, and strong acid carriers are uniformly distributed on the surface of the pore channels of the mesopores; the total pore volume of the catalyst carrier is 0.6-1.2 ml/g, and the specific surface area is 180-350 m2The pore volume of the mesopores accounts for 60-95% of the total pore volume of the catalyst carrier; based on oxidesThe catalyst contains 6.0-14.0 w% of MoO3Or WO31.0-5.0 w% of CoO or NiO, 0.05-5.0 w% of B2O3。
As an improved embodiment mode, the catalyst contains 6.5-12.0 w% of MoO3Or WO31.5 to 3.5 w% of CoO or NiO and 0.05 to 5.0 w% of B2O3。
As an improved embodiment mode, the specific surface area of the catalyst carrier is 200-330 m2/g。
As an improved embodiment mode, the total pore volume of the catalyst carrier is 0.70-1.0 ml/g.
As a modified embodiment, the catalyst support is alumina.
As an improved embodiment mode, the pore volume of the mesopores accounts for 70-95% of the total pore volume of the catalyst carrier.
A preparation method of a boron-containing residual oil hydrotreating catalyst comprises the following steps:
step 1): preparing a carrier: preparing an aluminum salt solution, mixing sol by adopting a pH swing method, adding an organic pore-enlarging agent solution containing a silicon compound in the mixing process, adding the organic pore-enlarging agent solution into a gel forming tank, forming gel at the temperature of between 60 and 90 ℃, aging, drying, forming and roasting at the temperature of between 550 and 1100 ℃ to obtain an alumina carrier after the gel forming is finished; the pH swing range is 4-10, and the pH value of the final reaction system is 8-10;
step 2): soaking an alumina carrier in Mo or W and Co or Ni impregnation liquid in the same volume, drying at the temperature of 90-150 ℃ for 2-8 hours, and roasting at the temperature of 600-800 ℃ for 1-5 hours to obtain a hydrodemetallization catalyst;
the hydrogenation demetallization catalyst contains MoO3Or WO3And NiO or CoO, the MoO3Or WO3The total mass of the NiO or the CoO accounts for 5.0-14.0% of the mass of the catalyst, and the total mass of the NiO or the CoO accounts for 1.0-5.0% of the mass of the catalyst.
As an improved embodiment mode, the organic pore-expanding agent in the step 1) is one or two of polystyrene spheres and polymethyl methacrylate spheres, and the diameter of the organic pore-expanding agent is 30-300 nm.
As an improved embodiment mode, the usage amount of the polystyrene spheres and/or the polymethyl methacrylate spheres is 10-20% calculated by taking the calcined alumina as a reference; the boron-containing compound is one or more of boric acid, sodium borate and ammonium borate.
As a modified embodiment mode, the impregnating solution in the step 2) is one of Mo-Ni, Mo-Co, W-Co and W-Ni solution.
For the above range values, end point values and intermediate values may be specifically employed.
In the preparation process of the carrier, the pore-expanding agent and the boron-containing compound which are introduced into the sol by adopting a PH swing method can be uniformly dispersed in the carrier, the boron-containing compound and the organic pore-expanding agent are introduced, the pore-expanding agent can be uniformly dispersed in the carrier in the sol-gel production process, the key effect is played on the uniform preparation of mesopores of the carrier, the boron-containing compound is loaded on the surface of the carrier in the pore channel forming process, boron-aluminum oxide can modulate the amount of B acid and L acid on the surface of the alumina carrier, the interaction between active metal of the catalyst and the carrier is mainly weakened, and the hydrogenation performance of the active metal of the catalyst is mainly improved, so that the prepared residual oil hydrodemetallization catalyst is more favorable for hydrogenation reaction and removal of metallic nickel compounds.
The pore structure properties of the carrier and the catalyst are measured by a PorematerMacro mercury intrusion instrument of Congta corporation, the crushing strength of the catalyst is measured by a BR 17-GCS catalyst particle crushing strength tester, and the content of metal in the oil product is measured by an atomic emission spectrometer.
The catalytic activity of the hydrodemetallization catalyst is evaluated on a trickle bed hydrogenation micro-reactor by using a certain vacuum residue raw material, and the catalytic activity is evaluated on a 100ml fixed bed reactor. Sampling after the hydrodemetallization reaction for 300 hours to determine the metallic nickel. The nickel content in the produced oil was determined by plasma emission spectroscopy (AES/ICP) and the sulfur content in the produced oil was determined by fluorescence.
The following examples further illustrate the invention.
The reagents used in the examples, except where specifically indicated, were all chemically pure reagents.
Examples 1 to 3 illustrate the preparation method of the catalyst carrier provided by the present invention.
Example 1
(1) Preparing a carrier: preparing 0.98M aluminum trichloride solution, under the condition of stirring, adding the aluminum trichloride solution and ammonia water into a gel forming tank in a concurrent flow manner by adopting a pH swing method, wherein the flow rate of the aluminum trichloride is 2.0ml/min, the temperature in the gel forming tank is controlled to be 70 ℃, the pH swing range is 4-10, and the pH value of a final reaction system is 8-10. And simultaneously adding a polystyrene ball pore-expanding agent solution containing a certain amount of boric acid for 2.0ml/min, wherein the total adding amount of the pore-expanding agent is 13 percent of the mass of the roasted alumina. After the cementing, aging for 0.5h, drying for 60h at 50 ℃ under the vacuum condition, extruding and molding, and roasting for 6h at 800 ℃ to obtain the load B2O3(1.5 w% based on the final catalyst content) of an alumina support B2O3/γ～Al2O3。
(2) Impregnation of active metal: according to MoO in the final catalyst3The content of the catalyst is 9.2 wt%, the content of NiO is 3.0%, a proper amount of ammonium heptamolybdate and nickel nitrate are weighed to prepare an aqueous solution, the carrier is impregnated by adopting an isometric impregnation method, the carrier is impregnated for 2 hours at 70 ℃, then the carrier is dried for 2 hours in vacuum at 120 ℃, and is roasted for 4 hours at 650 ℃ to obtain the catalyst MoO3-NiO-B2O3/γ～Al2O3Catalyst a 1.
Example 2
(1) Preparing a carrier: preparing a 1.0M aluminum trichloride solution, adding the aluminum trichloride solution and ammonia water into a gel forming tank in a concurrent flow manner by adopting a pH swing method under the stirring condition, wherein the flow rate of the aluminum trichloride is 2.0ml/min, the temperature in the gel forming tank is controlled to be 70 ℃, the pH swing range is 4-10, and the pH value of a final reaction system is 8-10. And simultaneously adding a polystyrene ball pore-expanding agent solution containing a certain amount of boric acid for 2.0ml/min, wherein the total adding amount of the pore-expanding agent is 15 percent of the mass of the roasted alumina. After the cementing process is finished,aging for 0.5h, drying at 50 deg.C for 60h under vacuum condition, extruding to form strips, and calcining at 800 deg.C for 6h to obtain B2O 3-loaded (2.0 w% of the final catalyst content) alumina carrier B2O3/γ～Al2O3。
(2) Impregnation of active metal: weighing a proper amount of ammonium heptamolybdate and nickel nitrate to prepare an aqueous solution according to the MoO3 content of 9.2 wt% and the NiO content of 3.0% in the final catalyst, impregnating the carrier by adopting an isometric impregnation method, impregnating for 2h at 70 ℃, then drying for 2h in vacuum at 120 ℃, roasting for 4h at 650 ℃, and obtaining the catalyst MoO3-NiO-B2O 3/gamma-Al2O3Catalyst a 2.
Example 3
(1) Preparing a carrier: preparing 1.1M aluminum trichloride solution, under the condition of stirring, adding the aluminum trichloride solution and ammonia water into a gel forming tank in a concurrent flow manner by adopting a pH swing method, wherein the flow rate of the aluminum trichloride is 2.0ml/min, the temperature in the gel forming tank is controlled to be 70 ℃, the pH swing range is 4-10, and the pH value of a final reaction system is 8-10. And simultaneously adding a polystyrene ball pore-expanding agent solution containing a certain amount of boric acid for 2.0ml/min, wherein the total adding amount of the pore-expanding agent is 17 percent of the mass of the roasted alumina. After the cementing, aging for 0.5h, drying for 60h at 50 ℃ under the vacuum condition, extruding and molding, and roasting for 6h at 800 ℃ to obtain the load B2O3(2.5 w% based on the final catalyst content) of an alumina support B2O3/γ～Al2O3。
(2) Impregnation of active metal: according to MoO in the final catalyst3The content of the catalyst is 9.2 wt%, the content of NiO is 3.0%, a proper amount of ammonium heptamolybdate and nickel nitrate are weighed to prepare an aqueous solution, the carrier is impregnated by adopting an isometric impregnation method, the carrier is impregnated for 2 hours at 70 ℃, then the carrier is dried for 2 hours in vacuum at 120 ℃, and is roasted for 4 hours at 650 ℃ to obtain the catalyst MoO3-NiO-B2O3/γ～Al2O3Catalyst a 3.
Comparative example 1
The procedure of example 1 was followed except that the solution containing the boron-containing compound and the organic pore-expanding agent was not added. The catalyst prepared was comparative catalyst D1.
The pore size distribution of the catalyst is shown in the table.
The properties of each vector are listed in table 1.
TABLE 1 Properties of the catalysts
| A1 | A2 | A3 | Comparative example D1 | |
| Pore volume of 10-30 nm, v% | 82.2 | 85.3 | 87.2 | 35.4 |
| MoO3，％ | 9.2 | 9.2 | 9.2 | 9.2 |
| NiO，％ | 3.0 | 3.0 | 3.0 | 3.0 |
| B2O3,％ | 1.5 | 2.0 | 2.5 | 0 |
The catalytic activity of the hydrodemetallization catalyst is evaluated on a trickle bed hydrogenation micro-reactor by using a certain vacuum residue raw material, and the catalytic activity is evaluated on a 100ml fixed bed reactor. The sulfidation and reaction conditions used are shown in table 2. Sampling after the hydrodemetallization reaction for 300 hours to determine the metallic nickel. The nickel content of the resulting oil was measured by plasma emission spectroscopy (AES/ICP) and the sulfur content of the resulting oil was measured by fluorescence, the results of which are shown in Table 3.
TABLE 2 evaluation of catalyst hydrodemetallization reaction Activity
TABLE 3 catalyst hydroprocessing performance data
| A1 | A2 | A3 | Comparative example D1 | |
| HDNi，％ | 63.6 | 64.2 | 65.3 | 45.2 |
| HDS，％ | 84.8 | 85.7 | 87.1 | 79.5 |
The hydrogenation performance data in table 3 show that the hydrotreating catalyst prepared by the method of the present invention has higher nickel removal performance and desulfurization activity compared to the contrast agent and the reference agent, which indicates that the mesoporous pore size is centrally distributed and uniform, and meanwhile, the catalyst subjected to in-situ acid modification in the pore channel formation process is beneficial to improving the nickel removal activity of the catalyst, has better desulfurization activity, and is beneficial to improving the overall effect of the residual oil hydrotreating graded catalyst.
Finally, it should be noted that the present invention is not limited to the above embodiments, and many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (10)
1. A boron-containing residuum hydroprocessing catalyst characterized by: the catalyst is provided with mesopores, the mesopores are distributed in a concentrated manner and are uniform in size, the pore diameter range of the mesopores is 10-30 nm, and strong-acid carriers are uniformly distributed on the surface of a pore passage of the mesopores; the total pore volume of the catalyst carrier is 0.6-1.2 ml/g, and the specific surface area is 180-350 m2The pore volume of the mesopores accounts for 60-95% of the total pore volume of the catalyst carrier; the catalyst contains 6.0-14.0 w% MoO based on oxide3Or WO31.0-5.0 w% of CoO or NiO, 0.05-5.0 w% of B2O3。
2. A boron-containing residuum hydroprocessing catalyst as recited in claim 1, characterized by: the catalystThe agent contains 6.5-12.0 w% of MoO3Or WO31.5 to 3.5 w% of CoO or NiO and 0.05 to 5.0 w% of B2O3。
3. A boron-containing residuum hydrotreating catalyst as claimed in claim 1 or 2 characterized in that: the specific surface area of the catalyst carrier is 200-330 m2/g。
4. A boron-containing resid hydrotreating catalyst as recited in claim 3, characterized in that: the total pore volume of the catalyst carrier is 0.70-1.0 ml/g.
5. A boron-containing resid hydrotreating catalyst as recited in claim 3, characterized in that: the catalyst carrier is alumina.
6. A boron-containing resid hydrotreating catalyst as recited in claim 3, characterized in that: the pore volume of the mesopores accounts for 70-95% of the total pore volume of the catalyst carrier.
7. A preparation method of a boron-containing residual oil hydrotreating catalyst is characterized by comprising the following steps:
step 1): preparing a carrier: preparing an aluminum salt solution, mixing sol by adopting a pH swing method, adding an organic pore-enlarging agent solution containing a titanium compound in the mixing process, introducing the organic pore-enlarging agent solution into a gel forming tank, forming gel at the temperature of between 60 and 90 ℃, aging, drying, forming and roasting at the temperature of between 550 and 1100 ℃ to obtain an alumina carrier after the gel forming is finished; the pH swing range is 4-10, and the pH value of the final reaction system is 8-10;
step 2): soaking an alumina carrier in Mo or W and Co or Ni impregnation liquid in the same volume, drying at the temperature of 90-150 ℃ for 2-8 hours, and roasting at the temperature of 600-800 ℃ for 1-5 hours to obtain a hydrodemetallization catalyst;
the hydrogenation demetallization catalyst contains MoO3Or WO3And NiO orCoO, said MoO3Or WO3The total mass of the NiO or the CoO accounts for 5.0-14.0% of the mass of the catalyst, and the total mass of the NiO or the CoO accounts for 1.0-5.0% of the mass of the catalyst.
8. The method for preparing a boron-containing residue hydrotreating catalyst according to claim 7, characterized in that: the organic pore-expanding agent in the step 1) is one or two of polystyrene spheres and polymethyl methacrylate spheres, and the diameter of the organic pore-expanding agent is 30-300 nm.
9. The method for preparing a boron-containing residue hydrotreating catalyst according to claim 8, characterized in that: the use amount of the polystyrene spheres and/or the polymethyl methacrylate spheres is 10-20% calculated by taking the roasted alumina as a reference; the boron-containing compound is one or more of boric acid, sodium borate and ammonium borate.
10. The method for preparing a boron-containing residue hydrotreating catalyst according to claim 1, characterized in that: the impregnation liquid in the step 2) is one of Mo-Ni, Mo-Co, W-Co and W-Ni mixed solution.
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