CN115245830B - Poor-quality residual oil hydrodemetallization catalyst and preparation method thereof - Google Patents

Poor-quality residual oil hydrodemetallization catalyst and preparation method thereof Download PDF

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CN115245830B
CN115245830B CN202110459132.0A CN202110459132A CN115245830B CN 115245830 B CN115245830 B CN 115245830B CN 202110459132 A CN202110459132 A CN 202110459132A CN 115245830 B CN115245830 B CN 115245830B
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catalyst
pore
hydrodemetallization
preparation
alumina
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CN115245830A (en
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程涛
张天琪
赵愉生
郑丽君
宋俊男
赵元生
崔瑞利
张全国
姚远
张涛
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Petrochina Co Ltd
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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
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J23/70—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
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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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  • Materials Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a catalyst for hydrodemetallization of inferior residuum and a preparation method thereof, wherein the preparation method comprises the following steps: mixing hydrated alumina with a powdery adhesive and an organic pore-expanding agent, adding an aqueous solution containing chemical pore-expanding agent, ammonia and low-carbon alcohol, kneading, forming, drying and roasting, and loading active metal to obtain a catalyst; the adhesive is synthetic cellulose, the organic pore-expanding agent is a water-soluble organic polymer, and the chemical pore-expanding agent is a boron-containing compound. The catalyst prepared by the method has a double-peak pore structure, has larger pore volume and pore diameter, has high demetallization activity and strong metal capacity, and is particularly suitable for the hydrotreatment of inferior heavy oil and residual oil.

Description

Poor-quality residual oil hydrodemetallization catalyst and preparation method thereof
Technical Field
The invention relates to a catalyst for hydrodemetallization of inferior residual oil and a preparation method thereof, in particular to a catalyst with high activity and high impurity capacity and capable of being used for hydrodemetallization of inferior heavy oil and a preparation method thereof.
Background
Currently, with the increasingly serious degradation and inferior quality of petroleum resources worldwide, as well as the urgent requirements for upgrading the quality of the petroleum products and the increasingly strict environmental regulations, there is an urgent need to develop clean and efficient heavy oil processing technologies. Hydrogenation is the most efficient heavy and residuum feedstock processing technique. Through hydrogenation, most of metal impurities and sulfur are removed, the carbon residue value is reduced, the quality of heavy oil is improved, and the possibility is provided for further efficient cleaning processing of the heavy oil. The combination of heavy oil and residual oil hydrotreatment and heavy oil catalytic cracking technology can maximally convert residual oil with low utilization value and easy environmental pollution, and greatly improve the light oil yield; and clean oil products with high added value and superior quality can be obtained. In a certain sense, the crude oil is converted by 100 percent, and the wish of completely eating and squeezing the crude oil in the petroleum refining process is realized. The technology combination becomes a core technology for improving economic benefit of sulfur-containing crude oil processing oil refining enterprises.
The deposition of Na, ca, ni, V and other metals in heavy oil on the hydrogenation catalyst can cause permanent poisoning, and is an important factor to be considered in the heavy oil hydrogenation process. Hydrodemetallization (HDM) catalysts are one of key technologies in heavy oil hydrotreating processes, and mainly serve to remove most of Ni, V and other metal impurities in raw materials, protect downstream desulfurization (HDS) and denitrification (HDN) catalysts, and have certain desulfurization capacity. The catalyst is required to have not only good metal removal capability but also higher metal impurity containing capability. Because most of the metal impurities in the residual oil exist in colloid and asphaltene, the colloid and asphaltene are the types with the largest molecular weight, the most complex structure and the strongest polarity in petroleum components, and have larger diffusion resistance. The demetallization agent is limited by the mass transfer and diffusion efficiency of the carrier, is easy to cause orifice blockage, has serious uneven deposition distribution of the removed impurities, and has limited metal holding capacity. All the above causes serious waste of the internal space of the catalyst, and the efficiency of the catalyst cannot be fully exerted. Therefore, the catalyst has larger pore volume, pore diameter and good pore channel permeability, so as to be beneficial to diffusion, reaction and deposition of macromolecular substances such as asphaltene and the like containing metal impurities in the residual oil raw material. One of the solutions is to adopt a carrier with a bimodal pore structure, wherein in the reaction process, macropores with the pore diameter of more than 100nm provide channels for the diffusion of macromolecular reaction substances, so as to promote the diffusion and deposition of impurities to the internal pore canal of the catalyst; and pore channels with the pore diameter below 50nm provide reaction surfaces and deposition sites for impurities. The two pore channels cooperate to enable the catalyst to have high demetallization activity and high impurity capacity.
CN1103009a discloses a preparation method of alumina carrier with double holes, which is prepared by mixing two kinds of alumina with different pore size distribution or its precursor, carbon black powder, surfactant, peptizing agent and water, drying and roasting. When the carbon black powder is used as a pore-enlarging agent, the pore-enlarging effect is poor, the strength of the carrier is low, and meanwhile, the pore volume and the pore diameter of the carrier can be reduced by adding the peptizer.
CN1120971 discloses a method for preparing alumina carrier with bimodal pore structure, which comprises uniformly mixing two or more pseudo-boehmite dry glue prepared by different raw material route methods, then peptizing, forming, drying and roasting. However, the method adopts an oil ammonia column method to mold the alumina carrier, has low production efficiency and large pollution in the production process, and is less adopted at present.
CN1647857a discloses a preparation method of macroporous alumina carrier, which comprises molding and roasting pseudo-boehmite composition containing organic pore-enlarging agent to obtain alumina carrier with bimodal pore structure. The method needs to pulp the organic pore-expanding agent and the pseudo-boehmite and spray-dry, and the preparation process is complex.
CN105983443B discloses a preparation method of a bimodal pore structure alumina carrier, which comprises the steps of mixing, forming and roasting an organic binder, a chemical pore-expanding agent and a physical pore-expanding agent to obtain the macroporous volume bimodal pore structure alumina carrier. The pore diameter of the carrier prepared by the method is limited to increase, the macropore proportion is greatly influenced by the addition amount of the pore-expanding agent, the carrier with larger pore diameter and macropore proportion cannot be prepared, the roasting temperature of the carrier is higher, and the production cost is high.
In the existing alumina carrier and catalyst preparation technology, acidic substances such as nitric acid, acetic acid, aluminum nitrate and the like are mostly required to be added as peptizers during the molding of the alumina, and the addition of the acidic substances can damage the particle structure of the alumina, so that the pore volume and the pore diameter of the carrier are reduced. The organic binder is used for replacing peptizing acid to form the carrier, so that the pore volume and the pore diameter of the carrier can be increased to a certain extent, but the effect is limited. The existing method simply increases the pore-enlarging agent when increasing the macropore proportion of the carrier, and the problems of increased cost, difficult molding, reduced strength and the like are faced when preparing the carrier with the high macropore proportion and the catalyst with the bimodal pore structure.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a preparation method of a residual oil hydrodemetallization catalyst with a bimodal pore structure, large pore volume and pore diameter and low cost.
In order to achieve the above purpose, the invention provides a preparation method of a catalyst for hydrodemetallization of inferior residuum, which comprises the following steps: mixing hydrated alumina with a powdery adhesive and an organic pore-expanding agent, adding an aqueous solution containing chemical pore-expanding agent, ammonia and low-carbon alcohol, kneading, forming, drying and roasting, and loading active metal to obtain a catalyst; the adhesive is synthetic cellulose, the organic pore-expanding agent is a water-soluble organic polymer, and the chemical pore-expanding agent is a boron-containing compound.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the water-soluble organic polymer is one or more selected from polyethylene glycol, polyacrylamide, polyvinyl alcohol and crosslinked povidone, and the addition amount of the catalyst is 1-6% of the weight of alumina.
The invention relates to a preparation method of a poor-quality residual oil hydrodemetallization catalyst, wherein a boron-containing compound is selected from one or more of boric acid, metaboric acid, ammonium hydrogen borate, ammonium tetraborate tetrahydrate and ammonium pentaborate tetrahydrate, and the addition amount of the boron-containing compound is 0.3-2% of the weight of aluminum oxide by using elemental boron.
The invention relates to a preparation method of a poor-quality residual oil hydrodemetallization catalyst, wherein the addition amount of ammonia is 0.05-0.5% of the weight of alumina.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the low-carbon alcohol is one or more selected from methanol, ethanol, glycol, propanol, isopropanol and glycerin, and the addition amount of the catalyst is 0.5-5% of the weight of alumina
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the active metal comprises a first active metal and/or a second active metal, the first active metal is molybdenum and/or tungsten, the second active metal is cobalt and/or nickel, the molybdenum and/or tungsten accounts for 2-8% of the total weight of the catalyst in terms of oxide, and the cobalt and/or nickel accounts for 0.4-2%.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the synthetic cellulose is one or more selected from methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, and the addition amount of the catalyst is 1-5% of the weight of alumina.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the viscosity of a 2% aqueous solution of synthetic cellulose is not lower than 50000 mPa.s.
The invention relates to a preparation method of a poor-quality residual oil hydrodemetallization catalyst, wherein the granularity of a water-soluble organic polymer is 80-400 meshes.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the molding process is carried out by adopting an oil pressure or hydraulic extrusion machine, and the extrusion pressure is 10-30 MPa.
The invention relates to a preparation method of a poor residual oil hydrodemetallization catalyst, wherein the roasting temperature is 500-1100 ℃ and the roasting time is 0.5-4 hours.
In order to achieve the aim, the invention also provides the poor-quality residual oil hydrodemetallization catalyst prepared by the method.
Compared with the prior art, the method provided by the invention does not use an acidic peptizing agent in the carrier forming process, so that the damage of acid to the hydrated alumina particle structure is reduced; the ammonia is added in a small amount, so that on one hand, the ammonia can effectively promote the compound reaming effect of the chemical reaming agent and the organic reaming agent, for example, the ammonia can promote the gelation reaction between boric acid and polyvinyl alcohol, the macropore proportion of more than 100nm in the carrier is effectively improved, and on the other hand, the ammonia can effectively reduce the bonding strength among alumina particles and increase the pore volume and pore diameter of the carrier; the low-carbon alcohol component is added, and the interaction between the boron-containing chemical pore-expanding agent and the organic pore-expanding agent is promoted by utilizing the solubility of the low-carbon alcohol to boric acid or the boron-containing compound and the affinity between the low-carbon alcohol and the organic pore-expanding agent, so that the boron-containing compound component is reduced to enter the inside of an alumina pore canal, more macroporous structures are generated, and the pore-expanding efficiency is improved; the addition amount of the organic pore-expanding agent is low, and the preparation cost is reduced.
The invention has the beneficial effects that:
The catalyst prepared by the method has a double-peak pore structure, has larger pore volume and pore diameter, has high demetallization activity and strong metal capacity, and is particularly suitable for the hydrotreatment of inferior heavy oil and residual oil. For example, the catalyst prepared according to the method provided by the invention has a specific surface area of 133 square meters per gram, a pore volume of 1.21 ml/g, characteristic peaks at 21 nm and 470 nm respectively, pores with pore diameters of 20-50 nm account for 38.9% of the total pore volume, pores with pore diameters of more than 100 nm account for 39.5% of the total pore volume, pores with pore diameters of less than 20nm account for 21.6% of the total pore volume, molybdenum oxide content of 4.3%, nickel oxide content of 1.3%; inferior middle east residual oil with the metal (Ni+V) content of 103 mug/g is used as a raw material, and the demetallization rate reaches 81.3% after 200 hours of reaction, 71.0% after 2000 hours of reaction and 65.8% after 4000 hours of reaction under the conditions of the reaction pressure of 16MPa, the reaction temperature of 380 ℃ and the airspeed of 1.0h < -1 >.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
The preparation method of the catalyst for hydrodemetallization of the inferior residuum comprises the following steps: mixing hydrated alumina with a powdery adhesive and an organic pore-expanding agent, adding an aqueous solution containing chemical pore-expanding agent, ammonia and low-carbon alcohol, kneading, forming, drying and roasting to obtain a carrier, and loading active metal to obtain a catalyst; the adhesive is synthetic cellulose, the organic pore-expanding agent is a water-soluble organic polymer, and the chemical pore-expanding agent is a boron-containing compound.
The shape of the carrier can be changed according to the needs, such as cylinder, clover, butterfly, five-tooth ball, etc. Proper amounts of extrusion aids (such as sesbania powder) and water can be added in the forming process.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the hydrated alumina is selected from one or more than one of gibbsite, boehmite, pseudo-boehmite and amorphous aluminum hydroxide. Preferably pseudo-boehmite. They may be commercially available or prepared by any of the methods known in the art. For example, the method adopts aluminum sulfate-sodium metaaluminate to prepare pseudo-boehmite.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the water-soluble organic polymer is one or more selected from polyethylene glycol, polyacrylamide, polyvinyl alcohol and crosslinked povidone, and the addition amount of the catalyst is 1-6% of the weight of alumina.
The invention relates to a preparation method of a poor-quality residual oil hydrodemetallization catalyst, wherein a boron-containing compound is selected from one or more of boric acid, metaboric acid, ammonium hydrogen borate, ammonium tetraborate tetrahydrate and ammonium pentaborate tetrahydrate, and the addition amount of the boron-containing compound is 0.3-2% of the weight of aluminum oxide by using elemental boron.
The invention relates to a preparation method of a poor-quality residual oil hydrodemetallization catalyst, wherein the addition amount of ammonia is 0.05-0.5% of the weight of alumina.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the low-carbon alcohol is one or more selected from methanol, ethanol, glycol, propanol, isopropanol and glycerin, and the addition amount of the catalyst is 0.5-5% of the weight of alumina
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the active metal comprises a first active metal and/or a second active metal, the first active metal is molybdenum and/or tungsten, the second active metal is cobalt and/or nickel, the molybdenum and/or tungsten accounts for 2-8% of the total weight of the catalyst in terms of oxide, and the cobalt and/or nickel accounts for 0.4-2%.
The active metal is loaded by a dipping mode, the active metal can be prepared into a stable metal solution by any known method, for example, ammonium heptamolybdate and nickel nitrate are added with ammonia water with a certain concentration under the stirring condition for dissolution, or molybdenum trioxide, basic nickel carbonate and phosphoric acid are dissolved together under the heating and stirring conditions, so that the stable metal solution can be prepared.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the synthetic cellulose is one or more selected from methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, and the addition amount of the catalyst is 1-5% of the weight of alumina.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the viscosity of a 2% aqueous solution of synthetic cellulose is not lower than 50000 mPa.s.
The invention relates to a preparation method of a poor-quality residual oil hydrodemetallization catalyst, wherein the granularity of a water-soluble organic polymer is 80-400 meshes.
The invention relates to a preparation method of a catalyst for hydrodemetallization of inferior residuum, wherein the molding process is carried out by adopting an oil pressure or hydraulic extrusion machine, and the extrusion pressure is 10-30 MPa.
The invention relates to a preparation method of a poor residual oil hydrodemetallization catalyst, wherein the roasting temperature is 500-1100 ℃ and the roasting time is 0.5-4 hours.
The catalyst for hydrodemetallization of inferior residuum prepared by the method.
The catalyst provided by the method has large pore volume and aperture and a bimodal pore structure, the pore volume is 0.8-1.6 ml/g as measured by mercury intrusion method, the pores with the pore diameter of 20-50 nanometers account for 30-70% of the total pore volume, the pores with the pore diameter of more than 100 nanometers account for 20-50% of the total pore volume, the proportion of the pores with the pore diameter of less than 20nm account for less than 30% of the total pore volume, and the BET specific surface area is 80-220 square meters/g.
The catalyst provided by the method has large pore volume and pore diameter and a bimodal pore structure, and can be used as an inferior residuum hydrotreating catalyst, in particular a residuum hydrodemetallization catalyst.
The following examples and comparative examples are provided to further illustrate the features of the present invention.
Example 1
Weighing 500g of macroporous pseudo-boehmite dry gel powder (dry basis content 71.5 wt%) produced by the Heng Hui chemical Co Ltd of a cigarette holder, adding 10.7g of hydroxypropyl methylcellulose with the viscosity of 15 ten thousand mPa.s (the viscosity of 2% aqueous solution) and 14.3g of polyvinyl alcohol powder with the granularity of 120 meshes, and uniformly mixing; dissolving 14.3g boric acid in 607.8g purified water, adding 5g ammonia water with concentration of 20% and 10g ethanol, stirring, slowly adding into the above materials, kneading into plastic body, extruding into clover with diameter of 1.6mm on an oil pressure extruder, and controlling extrusion pressure to 20MPa. Drying at 120deg.C for 2.0 hr, and placing into high temperature roasting furnace, and keeping the temperature at 900deg.C for 3 hr to obtain the carrier. Preparing a stable metal impregnation liquid containing (3.8 g MoO 3 plus 0.8g NiO)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature in a roasting furnace at 500 ℃ for 3 hours to obtain the catalyst A. The physical properties of the catalyst are shown in Table 1.
Example 2
500G of macroporous pseudo-boehmite dry gel powder (dry basis content 71.5 wt%) produced by the tobacco stand Henghui chemical industry Co., ltd is weighed, 3.6g of hydroxypropyl methylcellulose with the viscosity of 20 ten thousand mPa.s (the viscosity of 2% aqueous solution) is added, 11.5g of polyvinyl alcohol powder with the granularity of 80 meshes and 10.0g of polyethylene glycol powder with the granularity of 120 meshes are added, and the mixture is uniformly mixed; 20.4 g of ammonium tetraborate tetrahydrate is dissolved in 607.8g of purified water, 0.89g of ammonia water with concentration of 20 percent, 10g of ethylene glycol and 7.88g of methanol are added, uniformly stirred, slowly added into the materials, kneaded into a plastic body, extruded into clover with diameter of 1.6mm on an oil-pressure extruder, and extrusion pressure is controlled to be 10MPa. Then the mixture is put into a high-temperature roasting furnace, and the temperature is kept at 1100 ℃ for 0.5 hour, thus obtaining the carrier. Preparing a stable metal impregnation liquid containing (1.4 g MoO 3+1.4g Co2O3)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature in a roasting furnace at 500 ℃ for 3 hours to obtain the catalyst B. The physical properties of the catalyst are shown in Table 1.
Example 3
Weighing 500g of macroporous pseudo-boehmite dry gel powder (dry basis content 71.5 wt%) produced by the Heng Hui chemical Co Ltd of a cigarette holder, adding 17.9g of hydroxyethyl methylcellulose with the viscosity of 10 ten thousand mPa.s (the viscosity of 2% aqueous solution) and 17.9g of polyacrylamide with the granularity of 200 meshes, and uniformly mixing; 5.67g of ammonium hydrogen borate is dissolved in 607.8g of purified water, 8.94g of ammonia water with concentration of 20% and 1.79g of propanol are added, the mixture is stirred uniformly, the mixture is slowly added into the materials, kneaded into a plastic body, then the plastic body is extruded into clover with diameter of 1.6mm on an oil-pressure extruder, and the extrusion pressure is controlled to be 30MPa. Then the mixture is put into a high-temperature roasting furnace and kept at the temperature of 500 ℃ for 4 hours to obtain the carrier. Preparing a stable metal impregnation liquid containing (5.5 g WO 3+1.8g MoO3+0.9g NiO+0.5g Co2O3)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature of the impregnated material at 500 ℃ for 3 hours in a roasting furnace to obtain the catalyst C. The physical properties of the catalyst are shown in Table 1.
Example 4
500G of pseudo-boehmite is weighed, 6.7g of hydroxypropyl methylcellulose with the viscosity of 15 ten thousand mPas (the viscosity of 2% aqueous solution) and 4.0g of methylcellulose with the viscosity of 10 ten thousand mPas (the viscosity of 2% aqueous solution) are added, and 3.6 g of crosslinked povidone with the granularity of 160 meshes are uniformly mixed; 29.0g of metaboric acid is dissolved in 607.8g of purified water, 7.5g of ammonia water with concentration of 20% and 8g of isopropanol are added, uniformly stirred, slowly added into the materials, kneaded into a plastic body, extruded into clover with diameter of 1.6mm on an oil-pressure extruder, and the extrusion pressure is controlled to be 18MPa. Then the mixture is put into a high-temperature roasting furnace, and the temperature is kept at 800 ℃ for 3 hours, thus obtaining the carrier. Preparing a stable metal impregnation liquid containing (3.3 g MoO 3 +1.2g NiO)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature of the impregnated material at 500 ℃ for 3 hours in a roasting furnace to obtain the catalyst D. The physical properties of the catalyst are shown in Table 1.
Example 5
Weighing 500g of pseudo-boehmite, adding 10.7g of ethyl cellulose with the viscosity of 15 ten thousand mPas (the viscosity of 2% aqueous solution), 5.7g of polyvinyl alcohol powder with the granularity of 400 meshes and 5.0g of polyacrylamide with the granularity of 80 meshes, and uniformly mixing; 20.4g boric acid and 4.7g ammonium pentaborate tetrahydrate are dissolved in 607.8g purified water, 6g ammonia water with concentration of 20% and 15g glycerin are added, evenly stirred, slowly added into the materials, kneaded into a plastic body, extruded into clover shape with diameter of 1.6mm on an oil pressure extruder, and extrusion pressure is controlled to be 20MPa. Then the mixture is put into a high-temperature roasting furnace and kept at 950 ℃ for 2.5 hours to obtain the carrier. Preparing a stable metal impregnation liquid containing (4.7 g MoO 3 plus 0.3g NiO)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature in a roasting furnace at 500 ℃ for 3 hours to obtain the catalyst E. The physical properties of the catalyst are shown in Table 1.
Comparative examples 1-3 illustrate prior art methods and bimodal pore structured alumina supports prepared by prior art methods.
Comparative example 1
In this comparative example, an alumina support and a catalyst were prepared according to the method described in CN1103009 a.
34.1G of aluminum hydroxide dry rubber powder (containing 75% of aluminum oxide alkyl aluminum hydrolysate) and 39.3g of aluminum hydroxide powder prepared by an aluminum sulfate method are mixed, 4.7g of high wear-resistant carbon black, 3.5g of surfactant SA-20 and 2.1g of aluminum nitrate and 66 ml of water are added, fully ground and mixed, extruded into a clover shape with the diameter of 1.8 mm on a strip extruder, dried at 120 ℃ and baked for 4 hours at 600 ℃ to obtain the carrier. Preparing a stable metal impregnation liquid containing (14.0 g MoO 3 +2.9g NiO)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature of the impregnated material at 500 ℃ for 3 hours in a roasting furnace to obtain the catalyst F. The physical properties of the catalyst are shown in Table 1.
Comparative example 2
In this comparative example, an alumina support and a catalyst were prepared according to the method described in CN1647857 a.
The method comprises the steps of preparing a NaAlO 2 solution with the concentration of 200g of alumina/liter by adopting the reaction of aluminum hydroxide and aluminum hydroxide, simultaneously adding the solution and an aluminum sulfate solution with the concentration of 90g of alumina/liter into a2 liter gelling tank in a parallel flow mode, pre-adding 1.5 liter of water into the tank, adjusting the flow of the aluminum sulfate solution with the flow of sodium metaaluminate of 1.1 liter/hour, enabling the gelling pH value to be 8, and collecting slurry generated by gelling in an aging tank at the gelling temperature of 50 ℃. Adding sodium carbonate into the aging tank after collection to adjust the pH value to 10, aging for 50 minutes, filtering and washing to obtain the pseudo-boehmite wet filter cake. Mixing 6.5 kg of the wet filter cake with 20.5g of sesbania powder, pulping, spray drying at 600 ℃ at 145 ℃ at the inlet temperature, extruding the dried composition on an extruder to form strips, drying at 120 ℃ and roasting at 800 ℃ for 3.5 hours to obtain the carrier. Preparing a stable metal impregnation liquid containing (10.0 g MoO 3 +1.3g NiO)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature in a roasting furnace at 500 ℃ for 3 hours to obtain the catalyst G. The physical properties of the catalyst are shown in Table 1.
Comparative example 3
In this comparative example, an alumina support and a catalyst were prepared according to the method described in CN 105983443B.
Weighing 500g of macroporous pseudo-boehmite dry gel powder (dry basis content 71.5 wt%) produced by the Heng Hui chemical Co Ltd of a cigarette holder, adding 10.7g of hydroxypropyl methylcellulose with the viscosity of 15 ten thousand mPa.s (the viscosity of 2% aqueous solution) and 17.9g of polyvinyl alcohol powder with the particle diameter of 90-150 mu m, and uniformly mixing; 14.3 g of boric acid was dissolved in 390g of purified water, slowly added to the above materials, kneaded into a plastic body, and extruded into a clover shape with a diameter of 1.6mm on a front extrusion single screw extruder. Drying at 120deg.C for 2.0 hr, placing into roasting furnace, and keeping constant temperature at 800deg.C for 3 hr to obtain carrier. Preparing a stable metal impregnation liquid containing (5.0 g MoO 3 +1.1 gNiO)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature in a roasting furnace at 500 ℃ for 3 hours to obtain the catalyst H. The physical properties of the catalyst are shown in Table 1.
Comparative example 4
Weighing 500g of macroporous pseudo-boehmite dry gel powder (dry basis content 71.5 wt%) produced by the Heng Hui chemical Co Ltd of a cigarette holder, adding 10.7g of hydroxypropyl methylcellulose with the viscosity of 15 ten thousand mPa.s (the viscosity of 2% aqueous solution), and uniformly mixing; 58.8g boric acid was dissolved in 390g purified water, slowly added to the above materials, kneaded into a plastic body, and extruded into a clover shape with a diameter of 1.6mm on a front extrusion single screw extruder. Drying at 120deg.C for 2.0 hr, placing into roasting furnace, and keeping constant temperature at 800deg.C for 3 hr to obtain carrier. Preparing a stable metal impregnation liquid containing (8.1 g MoO 3 +1.7g NiO)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature of the impregnated material at 500 ℃ for 3 hours in a roasting furnace to obtain the catalyst I. The physical properties of the catalyst are shown in Table 1.
Comparative example 5
Weighing 500g of macroporous pseudo-boehmite dry gel powder (dry basis content 71.5 wt%) produced by the Heng Hui chemical Co Ltd of a cigarette holder, adding 10.7g of hydroxypropyl methylcellulose with the viscosity of 15 ten thousand mPa.s (the viscosity of 2% aqueous solution) and 58.8g of polyvinyl alcohol powder with the particle diameter of 90-150 mu m, and uniformly mixing; 390g of purified water was slowly added to the above materials, kneaded into a plastic body, and then extruded into a clover shape with a diameter of 1.6mm on a front extrusion single screw extruder. Drying at 120deg.C for 2.0 hr, placing into roasting furnace, and keeping constant temperature at 800deg.C for 3 hr to obtain carrier. Preparing a stable metal impregnation liquid containing (7.2 g MoO 3 +1.5g NiO)/100 mL, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature of the impregnated material at 500 ℃ for 3 hours in a roasting furnace to obtain the catalyst J. The physical properties of the catalyst are shown in Table 1.
TABLE 1 catalyst physicochemical Properties
The results in Table 1 show that compared with the comparative examples, the catalyst prepared by the method of the invention has obvious bimodal pore structure, and has large pore volume, large pore diameter and higher macroporous ratio above 100 nm. As can be seen from the comparison effect of the comparative example 3 and the example 1, the carrier obtained by the method has larger pore volume and pore diameter and higher macropore proportion, and can effectively reduce the addition amount of the pore-expanding agent, thereby being beneficial to reducing the production cost.
The catalyst of Table 1 was evaluated for activity stability under the conditions shown in Table 2 and the results shown in Table 3.
Table 2 catalyst evaluation conditions
Nature of raw oil Middle eastern residuum
Density (20 ℃ C.)/g.cm -3 0.99
(Ni+V)，μg.g-1 103
Process conditions
Reaction temperature, DEG C 380
Hydrogen partial pressure, MPa 16
Volume space velocity, h -1 1.0
Hydrogen/oil ratio 750
TABLE 3 catalyst Metal removal Rate (HD (Ni+V))
As shown in the evaluation results of Table 3, the catalyst of the present invention has higher demetallization activity, less activity decrease after long-term operation, good stability and high impurity capacity.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. The preparation method of the catalyst for hydrodemetallization of the inferior residuum is characterized by comprising the following steps of: mixing hydrated alumina with a powdery adhesive and an organic pore-expanding agent, adding an aqueous solution containing chemical pore-expanding agent, ammonia and low-carbon alcohol, kneading, forming, drying and roasting, and loading active metal to obtain a catalyst; the adhesive is synthetic cellulose, the organic pore-expanding agent is a water-soluble organic polymer, and the chemical pore-expanding agent is a boron-containing compound;
The water-soluble organic polymer is one or more selected from polyethylene glycol, polyacrylamide, polyvinyl alcohol and crospovidone, and the addition amount of the water-soluble organic polymer is 1-6% of the weight of the alumina;
The boron-containing compound is selected from one or more of boric acid, metaboric acid, ammonium hydrogen borate, ammonium tetraborate tetrahydrate and ammonium pentaborate tetrahydrate, and the addition amount of the boron-containing compound is 0.3-2% of the weight of the aluminum oxide by the simple substance boron;
The addition amount of ammonia is 0.05-0.5% of the weight of the alumina;
The low-carbon alcohol is one or more of methanol, ethanol, glycol, propanol, isopropanol and glycerin, and the addition amount of the low-carbon alcohol is 0.5-5% of the weight of the alumina;
The catalyst has a bimodal pore structure, the pore volume is 0.8-1.6 ml/g, the pores with the pore diameter of 20-50 nanometers account for 30-70% of the total pore volume, the pores with the pore diameter of more than 100 nanometers account for 20-50% of the total pore volume, the proportion of the pores with the pore diameter of less than 20 nanometers to the total pore volume is less than 30%, and the BET specific surface area is 80-220 square meters/g.
2. The method for preparing the poor residuum hydrodemetallization catalyst according to claim 1, wherein the active metals comprise a first active metal and/or a second active metal, the first active metal is molybdenum and/or tungsten, the second active metal is cobalt and/or nickel, the molybdenum and/or tungsten accounts for 2-8% of the total weight of the catalyst in terms of oxide, and the cobalt and/or nickel accounts for 0.4-2%.
3. The preparation method of the poor-quality residual oil hydrodemetallization catalyst according to claim 1, wherein the synthetic cellulose is one or more selected from methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, and the addition amount of the catalyst is 1-5% of the weight of the alumina.
4. The process for preparing a catalyst for hydrodemetallization of inferior residuum as claimed in claim 3, wherein the viscosity of 2% aqueous solution of said synthetic cellulose is not lower than 50000 mPa s.
5. The method for preparing the poor-quality residual oil hydrodemetallization catalyst according to claim 1, wherein the granularity of the water-soluble organic polymer is 80-400 meshes.
6. The method for preparing the catalyst for hydrodemetallization of inferior residuum as claimed in claim 1, wherein the molding process is carried out by an oil pressure or hydraulic extrusion machine, and the extrusion pressure is 10-30 MPa.
7. The method for preparing the poor-quality residual oil hydrodemetallization catalyst according to claim 1, wherein the roasting temperature is 500-1100 ℃ and the roasting time is 0.5-4 hours.
8. A poor residuum hydrodemetallization catalyst prepared by the process of any one of claims 1-7.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102728335A (en) * 2011-04-14 2012-10-17 中国石油化工股份有限公司 Preparation method of boron-modified alumina carrier
CN105983418A (en) * 2015-02-05 2016-10-05 中国石油天然气股份有限公司 Preparation method of TiO 2-containing macroporous residual oil hydrodemetallization catalyst
CN106914249A (en) * 2015-12-24 2017-07-04 中国石油天然气股份有限公司 Residual oil hydrodemetallization catalyst and preparation method thereof
CN108786833A (en) * 2017-05-02 2018-11-13 中国石油化工股份有限公司 A kind of heavy-oil hydrogenation catalyst and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102728335A (en) * 2011-04-14 2012-10-17 中国石油化工股份有限公司 Preparation method of boron-modified alumina carrier
CN105983418A (en) * 2015-02-05 2016-10-05 中国石油天然气股份有限公司 Preparation method of TiO 2-containing macroporous residual oil hydrodemetallization catalyst
CN106914249A (en) * 2015-12-24 2017-07-04 中国石油天然气股份有限公司 Residual oil hydrodemetallization catalyst and preparation method thereof
CN108786833A (en) * 2017-05-02 2018-11-13 中国石油化工股份有限公司 A kind of heavy-oil hydrogenation catalyst and preparation method thereof

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