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CN113117759B - Protective agent and preparation method and application thereof - Google Patents

Protective agent and preparation method and application thereof Download PDF

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Publication number
CN113117759B
CN113117759B CN201911414295.6A CN201911414295A CN113117759B CN 113117759 B CN113117759 B CN 113117759B CN 201911414295 A CN201911414295 A CN 201911414295A CN 113117759 B CN113117759 B CN 113117759B
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CN
China
Prior art keywords
protective agent
fiber
pore
pore volume
protectant
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CN201911414295.6A
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CN113117759A (en
Inventor
王欣
王志武
刘涛
安�晟
袁胜华
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Priority to CN201911414295.6A priority Critical patent/CN113117759B/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
    • B01J33/00—Protection of catalysts, e.g. by coating
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • 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
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • 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
    • 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)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a protective agent, a preparation method thereof and application thereof in a low-grade oil hydrotreatment process with high content of iron and/or calcium metal impurities. The composition of the protective agent comprises refractory fibers; wherein the refractory fibers are in disordered interweaving distribution, and the pore channels are mainly micron-sized pore channels. The preparation method of the protective agent comprises the following steps: the refractory fiber is mixed with a binder, water and optionally a pore-forming agent to form a plastic body, and the plastic body is molded, dried and baked to obtain the protective agent. The protective agent is beneficial to the reaction and deposition of metal impurities such as iron, calcium and the like in the raw oil entering the interior of the protective agent particles, and is also beneficial to the reaction and deposition of easily coked substances in the protective agent particles, so that on one hand, the protective effect of the protective agent on the downstream catalyst is fully exerted, on the other hand, the impurity deposition in the interior of the protective agent particles is high, the utilization rate of the protective agent is high, the impurity containing capability is strong, the rapid rise of bed pressure drop is prevented, and the running period of the device is prolonged.

Description

Protective agent and preparation method and application thereof
Technical Field
The invention relates to a macroporous material, in particular to a hydrogenation protecting catalyst suitable for petrochemical industry and a preparation method thereof.
Background
In the industries of oil refining, chemical industry and the like, when a fixed bed reactor is adopted to treat raw oil with heavy oil and the like and high impurity content, mechanical impurities in the raw oil and solid matters including metal sulfide, carbon deposit and the like generated by hydrogenation reaction partially enter a catalyst pore canal, and the other part is deposited in a catalyst bed layer outside catalyst particles. As the cumulative throughput of feedstock increases, catalyst activity decreases and even becomes completely inactive, catalyst bed pressure drop increases, product failure or the pressure drop becomes excessive and the unit is forced to shut down. This is because as the amount of processing increases, metal sulfides, carbon deposits and other solid impurity scales deposited in the catalyst bed gradually increase, a portion of the impurity scales enter the catalyst channels to deposit, resulting in a gradual increase in the content of solid deposits in the channels and apertures, and eventually the formation of aperture blocking, another portion of the deposits deposit between the catalyst particles, resulting in a gradual coverage of the catalyst surface as the content increases, and a decrease or even deactivation of the catalyst activity; in addition, the increase of solid sediment in the catalyst bed layer can lead to the decrease of the void ratio of the catalyst bed layer, the decrease of the bed layer is gradually increased, and the pressure drop can be rapidly increased after the critical value is reached to finally block the reactor. Therefore, in order to prolong the operation period of the device and ensure the activity of the main catalyst, a certain amount of protective agent is generally arranged on the main catalyst bed.
The existing protective agents are more in variety, the appearance of the protective agents is of various specifications such as spherical, columnar, raschig ring, impeller-shaped, honeycomb-shaped and cylindrical products, and the protective agents are mainly made of inert porous ceramic materials, inert alumina materials and alumina materials loaded with a certain amount of active metals. The main function of the protective agent is as follows: first, providing a deposition space for various solid deposits (such as mechanical impurities, carbon deposition, metal sulfides, etc.); second, filter, adsorb the fine solid impurity in the raw materials; thirdly, carrying out proper hydrogenation reaction on easily-coking components in the raw materials to delay the reduction of activity caused by carbon lamination of a main catalyst bed with high activity; fourth, remove impurity such as iron, calcium, vanadium, sodium, arsenic in raw materials, protect the downstream main catalyst, avoid poisoning and losing activity caused by heavy metal poisoning. According to the requirements of the protective agent, the protective agent has the characteristics of high void ratio, larger pore canal structure, proper hydrogenation activity and the like. At present, various protective agents have different shapes, sizes, materials and activities and different actions and effects. For example, the ceramic balls have high strength, but the void ratio of the ceramic balls is low, the specific surface area is small, so that the bed pressure is excessively reduced, the flow resistance of reactants is increased, and the effective contact rate of the reactants is reduced. For example, the ceramic ring has higher porosity, but the large hole exists in the center of the ceramic ring, so that the impurity interception capability is reduced, the treatment effect is affected, and the catalytic performance of the subsequent catalyst is affected.
The existing alumina carrier protective agent has a certain specific surface and hydrogenation activity, is large in Kong Zhanbi hours and is difficult to enter impurities such as iron, calcium and the like into the interior of catalyst particles to react and deposit because of the requirements of the molding technology and the strength of industrial operation catalyst particles, so that the outer surface of the protective agent is easily covered by impurity scales, and the catalyst is deactivated. For example, CN02133134.0 discloses a method for preparing an alumina carrier, which is obtained by mixing and shaping two pseudo-boehmite, and the pore diameter of the prepared carrier is concentrated in the range of 6nm-35nm and 100nm-2000 nm. The alumina carrier is suitable as a carrier of a hydrodemetallization catalyst with high activity, and is not suitable as a carrier of a hydrogenation protective agent. In addition, the strength of the protective agent is low, so that the use requirement cannot be met when the protective agent with high void ratio is prepared, and only the protective agent with relatively low void ratio can be prepared.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a protective agent, a preparation method and application thereof. The protective agent is particularly suitable for being used as a poor-quality oil hydrogenation protective agent with high iron and calcium content, is beneficial to the reaction and deposition of metal impurities such as iron, calcium and the like in raw oil entering the interior of protective agent particles, and is also beneficial to the reaction and deposition of easily coked substances in the protective agent particles, so that on one hand, the protective effect of the protective agent on a downstream catalyst is fully exerted, on the other hand, the impurity deposition in the interior of the protective agent particles is high, the protective agent has high utilization rate and strong impurity containing capacity, the bed pressure drop is prevented from being rapidly increased, and the running period of the device is prolonged.
The protective agent provided by the invention comprises refractory fibers; the refractory fibers are in disordered interweaving distribution, and the pore channels are mainly micron-sized pore channels.
Further, the refractory fiber has a diameter of 0.5-50 μm, a length of 5-500 μm, and an aspect ratio of 2-30.
Further, the refractory fiber is preferably as follows: the diameter is 1-20 μm, the length is 5-300 μm, and the length-diameter ratio is 2-20.
Further, the pore canal of the protective agent is mainly a micron-sized widely and continuously distributed open pore canal. In the present invention, the micro-scale pore means a pore having a pore diameter of 1000 μm or less and 1 μm or more. The pore canal of the protective agent is mainly a micron pore canal, and the pore volume of the pore canal outside the micron pore canal accounts for less than 1% of the total pore volume.
Further, the pore distribution of the protectant is as follows: the pore volume of the pores with the diameter smaller than 10 mu m is less than 10% of the total pore volume, the pore volume of the pores with the diameter of 10-100 mu m is 25% -50% (preferably 25% -40%) of the total pore volume, the pore volume of the pores with the diameter of 100-200 mu m is 25% -40% of the total pore volume, and the pore volume of the pores with the diameter larger than 200 mu m is 25% -40% of the total pore volume.
Further, the pore distribution of the protectant is as follows: the pore volume occupied by the pores with the pore diameter of more than 200 to 300 mu m is 12 to 35 percent of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 300 mu m is less than 20 percent of the total pore volume, preferably 2 to 20 percent.
Further, the protective agent may further comprise an active metal component. The active metal is a group VIB and/or a group VIII metal, preferably molybdenum and/or tungsten, and the group VIII metal is preferably cobalt and/or nickel.
Further, the content of the VIB group metal oxide is 1% -20% and the content of the VIII group metal oxide is 0.1% -8% based on the mass of the protective agent.
Further, the porosity of the protective agent is 65% -90%. Further, the mechanical strength of the protective agent is 50-500N/cm.
Further, the protective agent has the following properties: the specific surface area is 0.05-2.0 m 2 Per gram, pore volume of 0.1-06mL/g, bulk density of 0.5-1.5g/mL.
Further, the protective agent may further contain a binder component.
Further, the protectant may also contain conventional auxiliary components, such as at least one of phosphorus, boron, and the like.
Further, the refractory fiber may be at least one selected from the group consisting of diatomite fiber, rock wool fiber, mullite fiber, aluminum silicate fiber, quartz fiber, magnesia fiber, alumina fiber, carbon fiber, boron fiber, potassium titanate fiber, etc., preferably at least one selected from the group consisting of diatomite fiber, rock wool fiber, mullite fiber, aluminum silicate fiber, etc.
The preparation method of the protective agent provided by the invention comprises the following steps: the refractory fiber is mixed with binder, water and optionally pore-forming agent to obtain a plastic body, and the plastic body is molded, dried and baked to obtain the protective agent.
Further, the pore-forming agent may be optionally added, or may be added.
Further, in the preparation method of the protective agent, the pore-forming agent and further the pore-forming agent account for 5-150% of the weight of the refractory fiber.
Further, the binder is used in an amount of 0.5% -100% by weight of the refractory fiber.
Further, the pore-forming agent may be at least one of carbon black, graphite, paraffin wax, microcrystalline wax, various polymers (such as at least one of polyethylene, polypropylene, polystyrene, etc.), and the like. The pore-forming agent may be in the form of spheres, particles, powder, irregularities, etc. The particle size of the pore former may be from 3 to 2000 microns, preferably from 5 to 500 microns.
Further, the pore-forming agent may be an organic fiber, and has the following properties: diameter of 3-2000 microns (preferably 5-500 microns), length of 10-2000 microns, and length-diameter ratio of more than 1.
Further, the organic fiber is a fiber made of an organic material, and comprises at least one of natural fiber and artificial fiber. The natural fiber may be at least one of plant fiber and animal fiber. The plant fibers may be stem fibers, such as hemp fibers. The animal fiber can be at least one of wool fiber or silk, such as wool and silk. The artificial fiber may be at least one of polyester, acrylic, nylon, polypropylene, and high performance fiber including aramid, ultra high molecular weight polyethylene fiber (UHMWPE fiber), poly-p-phenylene benzobisoxazole fiber (PBO fiber), poly-p-benzimidazole fiber (PBI fiber), poly-phenylene pyridobisimidazole fiber (M5 fiber), polyimide fiber (PI fiber), etc.
Further, the molding may be performed by a conventional method such as extrusion or press molding. The shape can be various shapes such as column, sphere, ellipsoid, cylinder, bar, impeller, tooth sphere, other special shape, etc., wherein the protecting agent can be perforated, and the outer surface can be provided with grooves, etc.
Further, in the carrier molding process, at least one of extrusion aids, peptizing acid and other auxiliary agents can be added. The extrusion aid can be sesbania powder. The peptizing acid may be at least one of nitric acid, acetic acid, citric acid, etc.
Further, the binder may be an organic binder or an inorganic binder, and may be derived from at least one of acrylic acid, polyurethane, polystyrene, polyacrylate, ethylene-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, hydroxypropyl methylcellulose, starch, dextrin, polyvinyl alcohol, silicone, water glass, epoxy resin, silica sol, phosphoric acid, phosphate (such as aluminum phosphate), phosphoalumina gel, silicate, sulfate, borate, and the like.
Further, the drying condition of the carrier is that the carrier is dried for 2-8 hours at the temperature of 100-250 ℃, and the roasting condition of the carrier is that the carrier is roasted for 2-6 hours at the temperature of 600-1400 ℃.
Furthermore, the protective agent can also load active metal components to prepare the protective agent containing the active components.
Further, the active metal is a group VIB and/or a group VIII metal, preferably molybdenum and/or tungsten, and the group VIII metal is preferably cobalt and/or nickel.
Further, the content of the VIB group metal oxide is 1% -20% and the content of the VIII group metal oxide is 0.1% -8% based on the mass of the protective agent.
Further, in the protective agent containing the active component, the active metal loading method can adopt an impregnation method. After impregnation, drying and roasting are carried out to obtain the protective agent containing the active components. Wherein the catalyst is dried for 2-8 hours at 50-200 ℃ and baked for 2-6 hours at 400-800 ℃.
The protective agent is particularly suitable for being used as a heavy oil hydrogenation protective agent with high iron and/or calcium content and is used for removing impurities such as iron, calcium and the like in raw oil.
The invention also provides application of the protective agent in a hydrotreating process of low-quality oil (especially residual oil) with high iron and/or calcium content.
Further, in the inferior oil, the content of iron is 400 mug/g or less, and the content of calcium is 300 mug/g or less.
Further, the operating conditions for the hydrotreatment are as follows: the reaction temperature is 300-450 ℃, the hydrogen partial pressure is 10-18MPa, the hydrogen-oil volume ratio is 500-1500, and the liquid hourly space velocity is 0.1-30h -1 。
Further, the protective agent grading method adopts at least two protective agents, and the particle size is gradually reduced, the pore diameter is gradually reduced and the porosity is gradually reduced along the liquid phase flow direction.
Further, in the protective agent gradation method of the present invention, the protective agent I is preferably charged upstream of the protective agent of the present invention. The protective agent I is a protective agent with millimeter-sized pore canals and is mainly used for removing mechanical impurities in raw materials, and the protective agent I can be a filler-sized protective agent such as Raschig ring, pall ring and the like.
The protective agent is formed by interweaving refractory fibers into a micron-sized three-dimensional through continuous pore canal, which is beneficial to the reaction and deposition of metal impurities such as iron, calcium and the like in raw oil entering the interior of protective agent particles and the reaction and deposition of easily coked substances in the protective agent particles, so that on one hand, the protective effect of the protective agent on a downstream catalyst is fully exerted, on the other hand, the impurity is deposited in the interior of the protective agent particles, the utilization rate of the protective agent is high, the impurity containing capacity is strong, the rapid rise of bed pressure drop is prevented, and the running period of the device is prolonged.
The protective agent can be widely applied to hydrocracking, diesel hydrogenation, gasoline/naphtha hydrogenation, coal synthetic oil, coal tar hydrocracking, FCC pretreatment and other processes, can remove FeS, carbon particles, other mechanical impurities and the like, and has the functions of removing a proper amount of asphaltene, easy carbide hydrogenation and the like.
Drawings
FIG. 1 is a pore distribution diagram of the protectant obtained in example 1;
FIG. 2 is a graph showing the distribution of metal impurities after the protective agent obtained in example 1 is used;
FIG. 3 is a graph showing the distribution of metal impurities after the use of the protective agent FZC-11A of comparative example 1.
Detailed Description
The following describes the technical scheme of the present invention in detail with reference to examples.
The pore volume, specific surface, pore distribution and porosity in the present invention are measured by mercury intrusion. The crush strength was measured using an intensity meter. Bulk density was measured using a cylinder method. The samples were analyzed for Fe, ca and carbon content by X-ray fluorescence spectroscopy (AES/ICP) and infrared absorption.
Comparative example 1
In the protective reactor of the residual oil hydrogenation device, the upper part is filled with millimeter-level pore canal protective agent FZC-100, the lower part is filled with protective agent FZC-11A, and the filling volume ratio is 1:1. the properties of the vacuum residuum raw materials used are shown in Table 2, and the evaluation conditions and evaluation results of the protecting agent are shown in tables 3 and 5, respectively. After 12 months of operation, the reactor showed a significant increase in pressure drop.
The result of the electronic probe shows that impurities are intensively deposited on the surface and near surface, which proves that the conventional protective agent product has low utilization rate and is easy to cause the phenomena of blocking of the protective agent and rapid rise of pressure drop of a bed layer.
Example 1
10g of aluminum silicate fiber is selected and used for preparing the aluminum silicate fiber,adding 10g of binder, 8g of pore-forming agent and 44g of water, uniformly mixing to be plastic, preparing a four-impeller shape by an extrusion method, drying for 3 hours at 200 ℃, and roasting for 4 hours at 1100 ℃ to prepare the protective agent carrier. According to MoO 3 The protective agent is prepared by impregnating active metal with 5wt% of NiO and 2wt% of NiO, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 3 hours. The length of the aluminum silicate fiber is 20-50 micrometers, the diameter is 2-10 micrometers, the binder is 3g of 85wt% phosphoric acid, 1g of hydroxypropyl methyl cellulose and 2g of aluminum phosphate, the pore-forming agent is polypropylene small particles, and the granularity is 0.2-1mm. The prepared protective agent has the outer diameter of 5.5mm and the length of 6mm. The properties of the protectant are shown in Table 1.
The product particles of the embodiment are filled in a protection reactor (the protection reactor of the same comparative example 1) of a residual oil hydrogenation device, the millimeter-level pore canal protecting agent FZC-100 is filled at the upper part, the protecting agent of the embodiment is filled at the lower part, and the filling volume ratio is 1:1. the properties of the vacuum residuum raw materials used are shown in Table 2, and the evaluation conditions and the use effects and the evaluation results of the protecting agents are shown in tables 3, 4 and 5, respectively. After 18 months of operation, the reactor had no significant pressure drop rise.
The electron probe and the analysis result show that the product of the embodiment deposits impurity scale up to 330kg/m 3 The main components of the sediment are composed of metal sulfides such as carbon deposit, iron, calcium and the like, and the section of the particles shows that impurities enter the particles after operation, so that the overall utilization rate of the protective agent is high, the raw material has stronger impurity removing capability and higher scale containing capability, and the product of the embodiment can effectively inhibit rapid rise of bed pressure drop and improve the protective effect on downstream catalysts.
Comparative example 2
In the protection reactor of the hydrogenation device, FZC-100 is filled in the upper part, FZC-105 is filled in the lower part, and the filling volume ratio is 1:1. the properties of the raw materials are shown in Table 2, and the evaluation conditions and the evaluation results of the protective agent are shown in tables 3 and 5, respectively. After 3 months of operation, the reactor showed a significant increase in pressure drop and was forced to shut down.
The shutdown is caused by the fact that metallic impurities in the raw materials are intensively deposited on the surface and near the surface and quickly filled in the gaps among particles of the protective agent bed layer, and the pressure drop of the system is increased to the limit, so that the shutdown is forced.
Example 2
10g of aluminum silicate fiber, 7g of binder, 2g of pore-forming agent, 2g of glacial acetic acid, 1g of citric acid and 50g of purified water are added, uniformly mixed to be plastic, prepared into a seven-hole cylindrical shape by a pressing method, dried for 5 hours at 180 ℃, and then baked for 4 hours at 900 ℃ to prepare the protective agent carrier. According to MoO 3 3% of NiO and 0.3% of NiO are impregnated into active metal, dried for 3 hours at 150 ℃, and then baked for 5 hours at 450 ℃ to prepare the protective agent. The length of the aluminum silicate fiber is 30-70 microns, the diameter is 3-10 microns, the binder is 1g of acrylic acid, 5g of aluminum phosphate, the pore-forming agent is 2g of carbon black, and the particle size of the polystyrene is 4g (0.2-1 mm). The prepared protective agent has the diameter of 10mm and the thickness of 7mm.
The product particles of this example were packed in the guard reactor of a hydrogenation apparatus (guard reactor of comparative example 2), with FZC-100 packed in the upper part and the guard agent of this example packed in the lower part, in a packing volume ratio of 1:1. the properties of the raw materials are shown in Table 2, and the evaluation conditions and the use effects and the evaluation results of the protective agents are shown in tables 3, 4 and 5, respectively. The run time reached 12 months after loading with the protective agent of this example, and the reactor had no significant pressure drop rise.
The particles of the protective agent after operation are sampled and analyzed, and the deposition of the product of the embodiment contains impurities and dirt reaching 301kg/m 3 The main components of the sediment are carbon deposition, ferric sulfide and the like, the protective agent can enable various impurities to enter the pore canal to effectively deposit, hardening is avoided, the overall utilization rate of the catalyst is improved, the product of the embodiment has stronger impurity removing capability and higher scale containing capability on the inferior raw materials, the bed pressure drop can be effectively restrained from being quickly increased by using the product of the embodiment, the protection effect on downstream catalysts is improved, and the running period of the device is prolonged.
Example 3
10g of mullite fiber, 8g of binder, 5g of pore-forming agent and 15g of purified water are added, and the mixture is uniformly mixed to be plastic and passes throughThe preparation method is to prepare the impeller shape, the impeller shape is dried for 3 hours at 140 ℃, and then the impeller shape is roasted for 4 hours at 1200 ℃ to prepare the protective agent carrier. According to MoO 3 3wt% of NiO and 0.5wt% of impregnated active metal, drying at 120 ℃ for 5 hours, and roasting at 600 ℃ for 4 hours to obtain the protective agent. The mullite fiber has the length of 50-150 micrometers and the diameter of 3-10 micrometers, the binder is 4g of hydroxypropyl methyl cellulose, 1g of epoxy resin, 3g of polyvinyl alcohol and 2g of phosphoric acid, and the pore-forming agent is 5g of acrylic fiber and 2g of polyethylene small particles (the granularity is 0.2-1 mm). The prepared protective agent has the diameter of 8mm and the thickness of 5mm.
The protecting agent was evaluated for acceleration in a small-sized evaluation apparatus, the properties of the vacuum residue raw material used are shown in Table 2, and the conditions and effects of use of the protecting agent and the evaluation results are shown in tables 3, 4 and 5, respectively. And (5) stopping the operation for sampling after 5 months, and analyzing the impurity amount removed by the protective agent.
The main components of the sediment in the product of the embodiment are composed of carbon deposit, iron, calcium and other metal sulfides, the protective agent can enable various impurities to enter the inside of the pore canal to be effectively deposited, the overall utilization rate of the catalyst is improved, the rapid rise of bed pressure drop can be effectively restrained, the protection effect on downstream catalysts is improved, and the running period of the device is prolonged.
Comparative example 3
The conventional protectant FZC-11A was subjected to acceleration evaluation in a small-sized evaluation device, the properties of the used vacuum residue raw material are shown in Table 2, and the evaluation conditions and the evaluation results of the protectant are shown in tables 3 and 5, respectively. The operation is carried out for 3 months, the pressure drop of the system is increased, the system is forced to stop working, sampling is carried out, and the impurity amount removed by the protective agent is analyzed.
The shutdown is caused by the fact that metallic impurities in the raw materials are intensively deposited on the surface and near the surface and quickly filled in the gaps among particles of the protective agent bed layer, and the pressure drop of the system is increased to the limit, so that the shutdown is forced.
Example 4
10g of rock wool fiber, 4g of binder and 2g of purified water are added, the mixture is uniformly mixed to be plastic, the five-tooth ball shape is prepared by an extrusion-shaping method, and the weight of the mixture is 2Drying for 3 hours at the temperature of 00 ℃, and then roasting for 4 hours at the temperature of 700 ℃ to prepare the protective agent carrier. According to MoO 3 The protective agent is prepared by impregnating active metal with 8wt% of NiO and 1.5wt% of NiO, drying at 150 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours. The rock wool fiber has the length of 20-100 micrometers and the diameter of 2-10 micrometers, and the binder comprises 3g of acrylic resin, 3g of aluminum phosphate and 2g of hydroxypropyl methylcellulose. The diameter of the prepared protective agent is 6mm.
The protecting agent was evaluated for acceleration in a small-sized evaluation apparatus, the properties of the vacuum residue raw material used are shown in Table 2, and the conditions and effects of use of the protecting agent and the evaluation results are shown in tables 3, 4 and 5, respectively. And (5) after 4 months of operation, stopping the operation and sampling, and analyzing the impurity amount removed by the protective agent.
The main components of the sediment in the product of the embodiment are composed of carbon deposit, iron, calcium and other metal sulfides, the protective agent can enable various impurities to enter the inside of the pore canal to be effectively deposited, the overall utilization rate of the catalyst is improved, the rapid rise of bed pressure drop can be effectively restrained, the protection effect on downstream catalysts is improved, and the running period of the device is prolonged.
Example 5
10g of rock wool fiber, 4g of binder, 4g of pore-forming agent and 3g of purified water are added, the mixture is uniformly mixed to be plastic, the mixture is prepared into a five-tooth sphere shape by an extrusion-shaping method, the mixture is dried for 3 hours at 200 ℃, and then the mixture is baked for 4 hours at 700 ℃ to prepare the protective agent carrier. According to MoO 3 The protective agent is prepared by impregnating active metal with 8wt% of NiO and 1.5wt% of NiO, drying at 150 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours. The rock wool fiber has the length of 20-100 micrometers and the diameter of 2-10 micrometers, the pore-forming agent is polyethylene small particles (the granularity is 0.2-1 mm), and the binder is 3g of acrylic resin, 3g of aluminum phosphate and 2g of hydroxypropyl methylcellulose. The diameter of the prepared protective agent is 6mm.
The protecting agent was evaluated for acceleration in a small-sized evaluation apparatus, the properties of the vacuum residue raw material used are shown in Table 2, and the conditions and effects of use of the protecting agent and the evaluation results are shown in tables 3, 4 and 5, respectively. And (5) after 4 months of operation, stopping the operation and sampling, and analyzing the impurity amount removed by the protective agent.
The main components of the sediment in the product of the embodiment are composed of carbon deposit, iron, calcium and other metal sulfides, the protective agent can enable various impurities to enter the inside of the pore canal to be effectively deposited, the overall utilization rate of the catalyst is improved, the rapid rise of bed pressure drop can be effectively restrained, the protection effect on downstream catalysts is improved, and the running period of the device is prolonged.
TABLE 1 Properties of protectant
Project Example 1 Example 2 Example 3 Example 4 Example 5
Specific surface area, m 2 /g 0.287 0.070 0.321 1.224 0.391
Pore volume, mL/g 0.40 0.35 0.38 0.36 0.39
Bulk density, g/mL 0.60 0.70 0.62 0.68 0.63
Porosity% 74.2 73.0 71.7 65.5 70.5
Mechanical strength, N/cm 135 156 128 167 143
Pore distribution, percent
＜10μm 4 5 3 5 4
10-100μm 28 36 35 42 33
100-200μm 36 28 33 28 30
200-300μm 21 19 13 25 25
＞300μm 11 12 16 2 8
TABLE 2 Properties of the feedstock
Project Example 1/comparative example 1 Example 2/comparative example 2 Example 3/comparative example 3 Example 4 Example 5
Fe，μg/g 15 243 169 169 169
Ca，μg/g 3 - 131 131 131
Carbon residue, wt% 11.6 18 12.1 12.1 12.1
Table 3 evaluation conditions
Project Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Comparative example 3
Average reaction temperature, DEG C 375 360 390 390 390 375 360 390
Hydrogen partial pressure, MPa 17.0 16.5 14.7 15.7 15.7 17.0 16.5 14.7
Hydrogen to oil volume ratio 550 780 800 600 600 550 780 800
Liquid hourly space velocity, h -1 9.5 18 3.0 3.0 3.0 9.5 18 3.0
TABLE 4 effect of use
Project Example 1 Example 2 Example 3 Example 4 Example 5
Run time, month 18 12 5 4 4
Deposition amount of impurities, kg/m 3 330 301 385 378 354
Deposited impurity amount/fresh catalyst mass% 55.0 43.0 61.6 67.3 57.2
Whether the pressure drop is significantly increased Whether or not Whether or not Whether or not Whether or not Whether or not
Table 5 evaluation results
Project Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Comparative example 3
Run time, day 500 300 100 100 100 300 70 70
Impurity removal rate, percent
Fe 85.1 76.3 93.6 94.6 92.9 15.2 10.1 23.2
Ca 35.9 - 61.4 64.4 60.7 8.6 - 15.6
Carbon residue content, wt% 10.9 17.3 11.1 10.8 11.1 11.2 17.6 11.3

Claims (17)

1. A protective agent comprising refractory fibers and an active metal component; the refractory fibers are in disordered interweaving distribution, the pore channels are mainly micron-sized pore channels, and the pore distribution of the protective agent is as follows: the pore volume occupied by the pores with the diameter smaller than 10 mu m is less than 10% of the total pore volume, the pore volume occupied by the pores with the diameter of 10-100 mu m is 25% -50% of the total pore volume, the pore volume occupied by the pores with the diameter of 100-200 mu m is 25% -40% of the total pore volume, and the pore volume occupied by the pores with the diameter larger than 200 mu m is 25% -40% of the total pore volume; the pore canal of the protective agent is a micron-sized widely and continuously distributed open pore canal.
2. The protective agent according to claim 1, wherein the refractory fiber has a diameter of 0.5 to 50 μm, a length of 5 to 500 μm, and an aspect ratio of 2 to 30.
3. The protective agent according to claim 1, wherein the refractory fiber has a diameter of 1 to 20 μm, a length of 5 to 300 μm, and an aspect ratio of 2 to 20.
4. The protectant of claim 1, wherein the pores of the protectant are distributed as follows: the pore volume occupied by the pores with the pore diameter of more than 200 to 300 mu m is 12 to 35 percent of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 300 mu m is less than 20 percent of the total pore volume.
5. The protectant of claim 4, wherein the protectant has a pore distribution as follows: the pore volume occupied by pores with the pore diameter larger than 300 mu m is 2% -20% of the total pore volume.
6. The protectant of claim 1, wherein the protectant has a porosity of 65% to 90% and a mechanical strength of 50-500N/cm.
7. The protectant of claim 1, wherein the protectant has the following properties: the specific surface area is 0.05-2.0 m 2 Per g, pore volume of 0.1-0.6mL/g, and bulk density of 0.5-1.5g/mL.
8. The protective agent according to claim 1, wherein the refractory fiber is at least one selected from the group consisting of diatomaceous earth fiber, rock wool fiber, mullite fiber, aluminum silicate fiber, quartz fiber, magnesium oxide fiber, aluminum oxide fiber, carbon fiber, boron fiber, and potassium titanate fiber.
9. The protective agent according to claim 1, wherein the refractory fiber is at least one selected from the group consisting of diatomite fiber, rock wool fiber, mullite fiber, and aluminum silicate fiber.
10. The protective agent according to claim 1, characterized in that the active metal is a group vib and/or a group viii metal.
11. A protective agent according to claim 10, wherein the group vib metal is molybdenum and/or tungsten and the group viii metal is cobalt and/or nickel.
12. The protective agent according to claim 10, wherein the content of the group vib metal oxide is 1% to 20% and the content of the group viii metal oxide is 0.1% to 8% based on the mass of the protective agent.
13. The protectant of claim 1, wherein the protectant is in the form of a cylinder, sphere, ellipsoid, cylinder, bar, vane, or toothed sphere.
14. A protective agent according to claim 13, wherein the protective agent has grooves in the open and/or outer surface.
15. Use of a protecting agent according to any one of claims 1 to 14 in a process for the hydrotreatment of low-grade oils with high iron and/or calcium content.
16. The use according to claim 15, wherein a protecting agent I is filled upstream of the protecting agent, said protecting agent I being a protecting agent having millimeter-sized channels.
17. Use according to claim 15, characterized in that the inferior oil has an iron content of 400 μg/g or less and a calcium content of 300 μg/g or less.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101180121A (en) * 2005-05-25 2008-05-14 环球油品公司 Layered composition and processes for preparing and using the composition
CN101376830A (en) * 2007-08-27 2009-03-04 中国石油化工股份有限公司 Hydrotreating catalyst carrier and preparation thereof
CN101445260A (en) * 2008-12-26 2009-06-03 陕西科技大学 Multilayer meso-porous alumina fiber and preparation method thereof
CN103806990A (en) * 2014-02-11 2014-05-21 陕西理工学院 Method for preparing automobile exhaust processor with ceramic fiber catalyst carrier
CN109126768A (en) * 2018-09-29 2019-01-04 青岛华世洁环保科技有限公司 The integral catalyzer and preparation method thereof of the automobile-used vanadium tungsten titanium oxide carrying fiber of diesel oil

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101180121A (en) * 2005-05-25 2008-05-14 环球油品公司 Layered composition and processes for preparing and using the composition
CN101376830A (en) * 2007-08-27 2009-03-04 中国石油化工股份有限公司 Hydrotreating catalyst carrier and preparation thereof
CN101445260A (en) * 2008-12-26 2009-06-03 陕西科技大学 Multilayer meso-porous alumina fiber and preparation method thereof
CN103806990A (en) * 2014-02-11 2014-05-21 陕西理工学院 Method for preparing automobile exhaust processor with ceramic fiber catalyst carrier
CN109126768A (en) * 2018-09-29 2019-01-04 青岛华世洁环保科技有限公司 The integral catalyzer and preparation method thereof of the automobile-used vanadium tungsten titanium oxide carrying fiber of diesel oil

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