CN116983995A - Hydrogenation catalyst, preparation method and application thereof - Google Patents

Hydrogenation catalyst, preparation method and application thereof Download PDF

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Publication number
CN116983995A
CN116983995A CN202210448716.2A CN202210448716A CN116983995A CN 116983995 A CN116983995 A CN 116983995A CN 202210448716 A CN202210448716 A CN 202210448716A CN 116983995 A CN116983995 A CN 116983995A
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silicon
catalyst
metal
boehmite
polyimide
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Inventor
于秋莹
袁胜华
耿新国
隋宝宽
王永林
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Priority to CN202210448716.2A priority Critical patent/CN116983995A/en
Publication of CN116983995A publication Critical patent/CN116983995A/en
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • C10G2300/1077—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
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • 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)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a hydrogenation catalyst, a preparation method and application thereof. The catalyst comprises a polyimide/silicon-containing aluminum oxide composite carrier and active metal, wherein the mass ratio of polyimide to silicon-containing aluminum oxide in the composite carrier is 0.05-0.40, and the mass content of silicon oxide in the silicon-containing aluminum oxide is 5-40%. The residual oil hydrogenation catalyst provided by the invention is applied to residual oil hydrogenation treatment, has good desulfurization, denitrification and carbon residue removal performances, and particularly shows more excellent catalytic performance in the aspect of demetallization.

Description

Hydrogenation catalyst, preparation method and application thereof
Technical Field
The invention relates to a hydrogenation catalyst and a preparation method and application thereof, in particular to a hydrogenation catalyst and a preparation method and application thereof.
Background
The residual oil hydrogenation catalyst is mainly a metal supported catalyst, and alumina and/or silica are/is mainly used as a carrier, and Ni, mo, co and the like are used as active metal components. In the existing method, when the active metal load is large, the phenomenon of agglomeration or uneven distribution of metal particles is easy to occur. In addition, in the roasting process, the formation of metal-oxygen-aluminum bonds can be caused due to the strong interaction between the metal and the carrier, so that the catalytic efficiency of the catalyst is affected, and finally, the hydrogenation activity of the catalyst is reduced. The alumina carrier has proper amount of silica to raise the acidity and specific surface area of alumina, and to facilitate polymerization and hydrogenation reaction.
CN103055908A discloses a method for preparing a hydrotreating catalyst. Firstly pulping aluminum hydroxide or aluminum oxide to prepare slurry, and adding concentrated phosphoric acid to react to obtain sol; then taking the sol as a binder, kneading with macroporous alumina and small pore alumina, forming, drying and roasting to obtain an alumina carrier; then, the alumina carrier is impregnated with the active metal component impregnation liquid, and the hydrotreating catalyst is prepared by drying and roasting. The method is complex to operate, the introduction of acid sites can promote the bonding between active metal and a carrier, a large amount of concentrated acid can cause environmental pollution, and industrial production is dangerous.
CN105582945a discloses a method for preparing a hydrotreating catalyst. The method comprises the steps of firstly soaking an alumina carrier by using urea aqueous solution, then spraying and soaking the alumina carrier by using polyol or monosaccharide aqueous solution according to the sequence from high to low in concentration, so that the concentration of the polyol and/or monosaccharide is distributed on the carrier in a gradient manner from outside to inside, and then loading active metal components.
CN1257754a discloses a preparation method of a silica-alumina catalyst carrier, a silica-alumina precursor is prepared by introducing sodium silicate and aluminum sulfate, the pore volume of the prepared carrier is 0.45-0.75 mL/g, and the average pore diameter is 5-10nm. However, the final synthetic silica-alumina carrier has a smaller pore diameter and is not suitable for use as a hydrotreating catalyst for heavy oils or residues having a larger molecular weight.
CN1169614C discloses a preparation method of silicon-containing aluminum hydroxide, by introducing a certain amount of sodium silicate during the gelling process of preparing aluminum hydroxide by carbonization and continuing to add a certain amount of sodium silicate during the subsequent aging process, silicon-containing aluminum oxide can be prepared, which has a smaller average pore diameter, and although suitable for heavy oil or residual oil hydrodesulfurization or hydrodenitrogenation catalysts, the pore diameter is smaller for residual oil hydrodemetallization catalysts, which needs further improvement.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation catalyst, and a preparation method and application thereof. The catalyst provided by the invention has the advantages of higher metal loading, uniform dispersion, higher mechanical strength, proper pore distribution and specific surface area, proper surface acidity and suitability for residual oil hydrogenation treatment.
The first aspect of the invention provides a hydrogenation catalyst, which comprises a polyimide/silicon-containing aluminum oxide composite carrier and active metal, wherein the mass ratio of polyimide to silicon-containing aluminum oxide in the composite carrier is 0.05-0.40, and the mass content of silicon oxide in the silicon-containing aluminum oxide is 5% -40%, preferably 9.5% -17.0%.
In the catalyst, the active metal is at least one of group VIB metals and at least one of group VIII metals, wherein the group VIB metals are preferably at least one of Mo and W, more preferably Mo, and the group VIII metals are preferably at least one of Co and Ni, more preferably Ni.
In the catalyst, the content of the metal oxide of the VIB group is 15 to 25 percent and the content of the metal oxide of the VIII group is 1.9 to 5.6 percent based on the mass of the catalyst.
In the catalyst, the dispersity of the active metal is as follows: i VIB /I Al (. Times.100) is 2 to 6, I VIII /I Al (. Times.100) is 1 to 8.
In the invention, the specific surface area of the catalyst is 110-245 m 2 Preferably 195 to 225m 2 Per gram, the pore volume is 0.4-1.2 cm 3 And/g, the mechanical strength is 16-26N/mm, preferably 19-24N/mm, the pore volume of the pores with the pore diameter of 15-80 nm accounts for 3-20% of the total pore volume, and the pore volume of the pores with the pore diameter of less than 8nm accounts for less than 7%, preferably 3-6% of the total pore volume.
In the invention, the acid amount of the catalyst is 0.3-0.9 mmThe molar ratio of the catalyst to the aqueous solution is preferably 0.4 to 0.75mmol/g. Ratio C of the amount of acid B to the amount of acid L B /C L 0.02 to 0.09, preferably 0.055 to 0.088.
The second aspect of the present invention provides a method for preparing the hydrogenation catalyst, comprising the steps of:
(1) Preparing a polyimide material;
(2) Preparing a silicon-containing pseudo-boehmite wet filter cake, and drying to prepare the silicon-containing pseudo-boehmite;
(3) Mixing the polyimide material obtained in the step (1) with the silicon-containing pseudo-boehmite obtained in the step (2), forming, and drying to obtain a polyimide/silicon-containing aluminum oxide composite carrier;
(4) And (3) mixing the composite carrier prepared in the step (3) with a metal solution C, carrying out saturated impregnation, drying, and roasting in an inert atmosphere to obtain the catalyst.
In the method of the invention, in the step (2), the method for preparing the silicon-containing pseudo-boehmite wet filter cake comprises the following steps:
(A) Adding a first alkaline solution into a first reaction kettle, and introducing a mixed gas containing carbon dioxide to react so that the pH value of the system is 2-4;
(B) Adding bottom water into a second reaction kettle, heating to a reaction temperature, and then adding a second alkaline solution and the material obtained in the step (A) into the second reaction kettle in parallel flow for reaction;
(C) And (3) aging the slurry obtained after the reaction in the step (B), filtering and washing after the aging is finished to obtain the silicon-containing pseudo-boehmite filter cake.
In the method of the present invention, in the step (a), the first alkaline solution is one or two of a sodium metaaluminate solution or a potassium metaaluminate solution, preferably a sodium metaaluminate solution; the concentration of the sodium metaaluminate solution and/or the potassium metaaluminate is Al 2 O 3 10-30 g Al 2 O 3 and/L, wherein the caustic ratio of the first alkaline solution is 1.35-1.65.
In the method, in the step (A), the volume of the first alkaline solution added into the first reaction kettle is 2/3-3/4 of the volume of the first reaction kettle; the volume fraction of carbon dioxide in the carbon dioxide-containing mixed gas is 30% -70%; the carbon dioxide-containing mixed gas may be a mixed gas of carbon dioxide and air.
In the method of the invention, in the step (A), the initial reaction temperature of the reaction carried out by introducing the mixed gas containing carbon dioxide is 15-65 ℃, the reaction is exothermic, the temperature of the system is gradually increased, the whole reaction process does not need to be cooled to keep low temperature, and the temperature of the slurry is 40-75 ℃ at the end of the reaction.
In the method of the present invention, in the step (B), the second alkaline solution is a mixed solution of water glass and an aluminum-containing alkaline solution; the aluminum-containing alkaline solution is one or two of sodium metaaluminate solution or potassium metaaluminate solution, preferably sodium metaaluminate solution. The modulus of the water glass is 2.5-3.0, and the caustic ratio of the sodium metaaluminate solution or the potassium metaaluminate solution is 1.10-1.40, preferably 1.15-1.35.
In the method of the present invention, in the step (B), the concentration of the water glass in the second alkaline solution is SiO 2 5-95 g SiO 2 and/L, the concentration of sodium metaaluminate and/or potassium metaaluminate in the second alkaline solution is Al 2 O 3 130-350 g Al 2 O 3 Preferably 150 to 250g Al 2 O 3 /L。
In the method of the invention, in the step (B), the bottom water added into the second reaction kettle is 1/10-1/5 of the volume of the second reaction kettle.
In the method, in the step (B), the materials obtained in the step (A) are added into a second reaction kettle, and the material adding time is controlled to be 60-150 min. Further, in the step (B), the second alkaline solution and the material obtained in the step (A) are added into a second reaction kettle in parallel flow for reaction, and the pH value is controlled to be 7.5-9.0.
In the process of the present invention, in step (B), the reaction temperature of the reaction is 40℃to 70℃and preferably 45℃to 65 ℃.
In the process of the present invention, in step (B), the reaction is carried out with stirring.
In the method of the present invention, in the step (C), the aging conditions are: the temperature is 50-95 ℃ and the time is 30-20 min.
In the process of the present invention, in step (C), the washing may be carried out by a washing method conventional in the art, preferably by deionized water at 50℃to 80℃to neutrality.
In the method of the invention, in the step (C), the solid content of the obtained silicon-containing pseudo-boehmite wet filter cake is 35-45 wt%.
Further, in the step (1), the synthesis of the polyimide material includes:
(a) Dissolving p-diaminobenzene in N, N-dimethylformamide solution, then adding pyromellitic dianhydride, and stirring to obtain viscous solution;
(b) Transferring the solution into a reaction kettle, heating, cooling, cleaning with an organic solvent, drying, and grinding;
(c) And roasting the obtained powder sample under the protection of inert gas to obtain the polyimide material.
In the process of the present invention, in step (a), the concentration of p-diaminobenzene in the N, N-dimethylformamide solution is 0.005 to 0.1g/mL, preferably 0.01 to 0.05g/mL.
In the method of the present invention, in the step (a), the concentration of pyromellitic dianhydride in the N, N-dimethylformamide solution is 0.01 to 0.2g/mL, preferably 0.02 to 0.1g/mL.
In the process of the present invention, in step (a), the stirring time is 2 to 24 hours, preferably 6 to 10 hours.
In the process of the present invention, in step (b), the heating temperature is 130 to 300 ℃, preferably 160 to 190 ℃, for 4 to 15 hours.
In the method of the present invention, in the step (b), the organic solvent is one of N, N-dimethylformamide or toluene, preferably N, N-dimethylformamide, and the number of times of washing is 2 to 6.
In the method of the present invention, in the step (b), the drying temperature is 100 to 120 ℃ and the time is 2 to 5 hours.
In the process of the present invention, in step (c), the inert atmosphere is selected from Ar, he, N 2 At least one of (a) and (b); said bakingThe firing temperature is 250-600 ℃, preferably 300-400 ℃ and the time is 4-15 h.
In the method of the invention, in the step (2), the drying temperature is 60-150 ℃ and the drying time is 4-10 h. The dry basis content of the pseudo-boehmite obtained after drying is 75-85 wt%.
In the method, in the step (3), the mass ratio of the polyimide material obtained in the step (1) to the silicon-containing pseudo-boehmite is 0.05-0.30. The molding can be extrusion molding. An extrusion aid can be added in the forming process, the extrusion aid can be sesbania powder, and the addition amount of the extrusion aid is 1-6% of the mass of the silicon-containing pseudo-boehmite.
In the method, in the step (3), the drying temperature is 80-120 ℃ and the time is 4-6 h.
In the method of the invention, in the step (4), the impregnation adopts saturated impregnation; the active metal in the active metal solution C is selected from at least one of VIB group metals and at least one of VIII group metals, wherein the VIB group metals are preferably at least one of Mo and W, more preferably Mo, the VIII group metals are preferably at least one of Co and Ni, more preferably Ni, the concentration of the VIB group metals in terms of oxide is 0.15-0.4 g/mL, and the concentration of the VIII group metals in terms of oxide is 0.02-0.09 g/mL.
In the method of the present invention, in the step (4), the drying temperature is 80 to 120 ℃, the drying time is 2 to 5 hours, the baking temperature is 600 to 900 ℃, the baking time is 3 to 5 hours, and the baking is performed in an inert atmosphere (such as N 2 ) Is performed in the middle (a).
The third aspect of the invention provides the application of the hydrogenation catalyst in a residual oil hydrogenation process.
In the present invention, the residuum and hydrogen-containing gas are contacted and reacted under hydrogenation conditions in the presence of the hydrogenation catalyst described above or a hydrogenation catalyst obtained according to the above-described production method.
In the residual oil hydrogenation reaction, the residual oil material is selected from one of atmospheric residual oil, vacuum residual oil and high-temperature coal tar.
In the above-mentioned residuum hydrogenation reaction, the hydrogen-containing gas is hydrogen or a mixed gas of hydrogen and other gases, and the hydrogen volume content in the mixed gas is generally not less than 80%, preferably not less than 85%, and more preferably not less than 95%.
In the residuum hydrogenation process, the residuum hydrogenation operation conditions are as follows: the reaction pressure is 5-20 MPaG, the reaction temperature is 280-400 ℃, and the liquid hourly space velocity is 0.1-3.0 h- 1 The volume ratio of the hydrogen oil is 100-1000.
Compared with the prior art, the invention has the following beneficial effects:
the hydrogenation catalyst provided by the invention has the advantages of uniform dispersion of active metal, higher mechanical strength, proper pore distribution and specific surface area, proper surface acidity, good desulfurization, denitrification and carbon residue removal performances when being applied to residual oil hydrogenation treatment, and particularly shows more excellent catalytic performance in the aspect of demetallization.
According to the preparation method of the catalyst, the high polymer polyimide contains C, N, O element, after roasting, the band gap of the organic carbon material is opened to become a semiconductor material, then the semiconductor material is mixed with the silicon-containing pseudo-boehmite, the extruded strip is immersed in a metal solution, as a metal-semiconductor heterojunction is formed on the contact interface of the active phase metal and the polyimide, the migration rate of electrons between the active metal and the polyimide is accelerated by the heterojunction, and meanwhile, the interaction force between the active metal and the polyimide is enhanced, so that the active metal is more prone to being loaded on the surface of the polyimide in the loading process, the metal dispersibility is effectively improved, the adsorption and bonding effects between the active metal and the silicon-containing aluminum oxide carrier can be greatly weakened, and the activity of the synthesized catalyst is higher in the residual oil hydrogenation process. Further, the size of the interaction force between the active metal and the polyimide can be adjusted by adjusting the baking temperature of the polyimide and adjusting the size of the band gap. The nitrogen element contained in the polyimide can play a role in regulating the surface acidity of the catalyst during the subsequent baking process. In addition, the silicon-containing pseudo-boehmite wet filter cake gibbsite prepared by the method has low gibbsite, high crystallinity and easily-adjusted silicon content, and the silicon-containing aluminum oxide obtained by roasting has larger pore volume and pore diameter; meanwhile, the silica-containing pseudo-boehmite wet filter cake prepared by the method has high peptization index, and provides a guarantee for preparing the high-side pressure strength carrier.
Detailed Description
In the invention, a nitrogen adsorption and desorption curve of a sample is tested by adopting an ASAP2020 type full-automatic physical adsorption instrument of Micromeritics company in the United states at the temperature of minus 196 ℃, and the specific surface area, pore volume and pore diameter distribution are measured.
In the invention, the mechanical strength is tested by using a ZQJ-III intelligent particle strength tester manufactured by Dalian Chi taking tester, and the average mechanical strength of a group of samples with the length of 4-6mm is measured.
In the invention, the metal dispersity is measured by XRS (the instrument is model Kratos Axis Ultra DLD) to measure XPS peak intensity ratio of active metal and aluminum element.
In the invention, the infrared acid amount is measured by using a Nicolet 870 type Fourier transform infrared spectrometer of Nicolet company in the United states.
The technical scheme and effect of the present invention will be further described with reference to the following examples, but is not limited to the following examples.
Example 1
(1) A first 5000mL reactor was charged with Al having a caustic ratio of 1.45 and a concentration of 25g 2 O 3 The mixed solution of sodium metaaluminate of/L, then let in the mixed gas comprising carbon dioxide and air of 55% of the volume fraction of carbon dioxide, make system pH value drop to 3.4, the temperature of the supplies is 55 deg.C at the end of the reaction;
adding 1500mL of bottom water into 10000mL of second reaction kettle, starting a stirring and heating device, adding the materials into the second reaction kettle at a flow rate of 35mL/min when the temperature is raised to 65 ℃ for 90min, and adding 3500mL of SiO with a modulus of 2.8 and a concentration of 50g in parallel flow 2 Water glass/L and concentration of 180gAl 2 O 3 Sodium metaaluminate solution with 1.25 caustic ratio, controlling the pH value of the slurry in the second reaction kettle to 8.0 by adjusting the flow rate of the sodium metaaluminate solution, keeping the temperature of the slurry in the second reaction kettle constant, finishing the reaction after the materials are used up, aging the slurry at 90 ℃ for 80min, and using the temperature of 70 ℃ for deionization after the aging is finishedWashing with subwater to neutrality, filtering to obtain wet cake of silicon-containing pseudo-boehmite with solid content of 42%, and drying at 120 deg.c for 6 hr to obtain the required silicon-containing pseudo-boehmite.
(2) 100mmol of p-diaminobenzene was dissolved in 60mL of N, N-dimethylformamide, and 2.2g of pyromellitic dianhydride was added at the same time, followed by rapid stirring for 8 hours until the solution was viscous. Then transferring the solution into a hydrothermal reaction kettle, heating for 10 hours at 180 ℃, after cooling, flushing with N, N-dimethylformamide solvent for 3 times, drying for 4 hours at 110 ℃, and grinding for later use. And roasting the powder sample for 8 hours under the protection of nitrogen, wherein the roasting temperature is 350 ℃, and obtaining the polyimide carrier.
(3) 100g of polyimide sample is weighed, mixed with 500g of silicon-containing pseudo-boehmite (dry basis content 80%) and 15g of sesbania powder, extruded, and dried at 120 ℃ for 4 hours to obtain the composite carrier.
(4) Preparing MoO-containing 3 The composite carrier is saturated impregnated by impregnating solution with 0.280g/mL and 0.077g/mL of NiO, dried for 5 hours at 120 ℃ after the impregnation is completed, baked for 3 hours at 650 ℃, and then nitrogen is introduced for protection, so that the final hydrogenation catalyst A is obtained, and the physicochemical properties of the final hydrogenation catalyst A are shown in Table 1.
Example 2
The synthesis process was the same as that of example 1 except that the polyimide addition amount was changed to 150g, to obtain a final hydrogenation catalyst B, the physicochemical properties of which are shown in Table 1.
Example 3
Other synthetic procedures were the same as in example 1 except that SiO was contained in the mixed solution in the preparation of pseudo-boehmite in step (1) 2 The concentration of Al in the first reaction kettle is changed to 75g/L 2 O 3 The concentration of (2) is changed to 15g/L, the volume fraction of carbon dioxide in the mixed gas of carbon dioxide and air is 45%, and the aging temperature is changed to 95 ℃ to obtain the silicon-containing pseudo-boehmite required by the example. The final hydrogenation catalyst C was obtained, and its physicochemical properties are shown in Table 1.
Example 4
Other synthesis procedures were the same as in example 1 except that in step (3), 40g of polyimide sample was weighed, mixed with 500g of silicon-containing pseudo-boehmite (dry basis content: 80%), and 15g of sesbania powder, and then extruded. The physicochemical properties of the final hydrogenation catalyst D obtained are shown in Table 1.
Comparative example 1
Other synthesis procedures were the same as in example 1 except that polyimide was replaced with an equivalent amount of activated carbon powder. The final hydrogenation catalyst E was obtained, the physicochemical properties of which are shown in Table 1.
Comparative example 2
Other synthesis procedures were the same as in example 1 except that the pseudo-boehmite preparation in step (1) was different in that 3000mL of 65gAl was added to a 5.0L reaction vessel 2 O 3 And (3) introducing mixed gas of carbon dioxide with the carbon dioxide content of 80% (volume fraction) and air into the sodium metaaluminate solution with the caustic ratio of 1.35, wherein the initial reaction temperature is 25 ℃, cooling the solution to maintain the slurry temperature unchanged, and controlling the reaction time to be 45min to reduce the pH value of the sodium metaaluminate solution to 8.8. The slurry was filtered, washed with deionized water at 75 ℃ and dried at 120 ℃ for 6 hours after the washing was completed to obtain pseudo-boehmite. The final hydrogenation catalyst F was obtained, and its physicochemical properties are shown in Table 1.
Example 5
The catalysts obtained in examples 1-4 and comparative examples 1-2 were used in residuum hydrogenation reactions, respectively, the feedstock properties are shown in Table 2, and the evaluation conditions and evaluation results are shown in Table 3.
TABLE 1 physicochemical Properties of hydrogenation catalysts
TABLE 2 oil Properties of raw materials
Table 3 evaluation conditions and evaluation results of the hydrogenation catalysts obtained in each example

Claims (13)

1. A hydrogenation catalyst comprises a polyimide/silicon-containing aluminum oxide composite carrier and active metals, wherein the mass ratio of polyimide to silicon-containing aluminum oxide in the composite carrier is 0.05-0.40, and the mass content of silicon oxide in the silicon-containing aluminum oxide is 5-40%, preferably 9.5-17.0%.
2. The catalyst according to claim 1, characterized in that the active metal is at least one of a group VIB metal, preferably at least one of Mo, W, more preferably Mo, and at least one of a group VIII metal, preferably Co, ni, more preferably Ni.
3. The catalyst according to claim 1, wherein the content of group VIB metal oxide in the catalyst is 15% -25% and the content of group VIII metal oxide is 1.9% -5.6% based on the mass of the catalyst.
4. The catalyst of claim 1, wherein the catalyst has an active metal dispersity of: i VIB /I Al (. Times.100) is 2 to 6, I VIII /I Al (. Times.100) is 1 to 8.
5. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 110-245 m 2 Preferably 195 to 225m 2 Per gram, the pore volume is 0.4-1.2 cm 3 And/g, the mechanical strength is 16-26N/mm, preferably 19-24N/mm, the pore volume of the pores with the pore diameter of 15-80 nm accounts for 3-20% of the total pore volume, and the pore volume of the pores with the pore diameter of less than 8nm accounts for less than 7%, preferably 3-6% of the total pore volume.
6. Root of Chinese characterCatalyst according to claim 1, characterized in that the acid amount of the catalyst is 0.3-0.9 mmol/g, preferably 0.40-0.75 mmol/g; ratio C of the amount of acid B to the amount of acid L B /C L 0.02 to 0.09, preferably 0.055 to 0.088.
7. A process for preparing the catalyst of any one of claims 1 to 6, comprising the steps of:
(1) Preparing a polyimide material;
(2) Preparing a silicon-containing pseudo-boehmite wet filter cake, and drying to prepare the silicon-containing pseudo-boehmite;
(3) Mixing the polyimide material obtained in the step (1) with the silicon-containing pseudo-boehmite obtained in the step (2), forming, and drying to obtain a polyimide/silicon-containing aluminum oxide composite carrier;
(4) And (3) mixing the composite carrier prepared in the step (3) with a metal solution C, carrying out saturated impregnation, drying, and roasting in an inert atmosphere to obtain the catalyst.
8. The method of claim 7, wherein the synthesis of the polyimide material in step (1) comprises:
(a) Dissolving p-diaminobenzene in N, N-dimethylformamide solution, then adding pyromellitic dianhydride, and stirring to obtain viscous solution;
(b) Transferring the solution into a reaction kettle, heating, cooling, cleaning for several times with an organic solvent, drying, and grinding;
(c) And roasting the obtained powder sample under the protection of inert gas to obtain the polyimide material.
9. The method of preparing a siliceous pseudo-boehmite wet cake according to claim 7, wherein the method of preparing a siliceous pseudo-boehmite wet cake in step (2) comprises:
(A) Adding a first alkaline solution into a first reaction kettle, and introducing a mixed gas containing carbon dioxide to react so that the pH value of the system is 2-4;
(B) Adding bottom water into a second reaction kettle, heating to a reaction temperature, and then adding a second alkaline solution and the material obtained in the step (A) into the second reaction kettle in parallel flow for reaction;
(C) And (3) aging the slurry obtained after the reaction in the step (B), filtering and washing after the aging is finished to obtain the silicon-containing pseudo-boehmite filter cake.
10. The method according to claim 7, wherein in the step (3), the mass ratio of the polyimide material to the silicon-containing pseudo-boehmite is 0.05 to 0.30.
11. The method of claim 7, wherein in step (4), the impregnation is saturated impregnation; the active metal in the active metal solution C is selected from at least one of VIB group metal and at least one of VIII group metal, wherein the VIB group metal is preferably at least one of Mo and W, more preferably Mo, and the VIII group metal is preferably at least one of Co and Ni, more preferably Ni; wherein the concentration of the VIB group metal in terms of oxide is 0.15-0.4 g/mL, and the concentration of the VIII group metal in terms of oxide is 0.02-0.09 g/mL.
12. The method according to claim 7, wherein in the step (4), the baking temperature is 600 to 900 ℃ and the baking time is controlled to 3 to 5 hours, and the baking is performed in an inert atmosphere.
13. Use of the hydrogenation catalyst according to any one of claims 1-6 in residuum hydrogenation processes.
CN202210448716.2A 2022-04-26 2022-04-26 Hydrogenation catalyst, preparation method and application thereof Pending CN116983995A (en)

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