CN108393091B - Coal liquefaction oil hydrotreating catalyst and preparation method and application thereof - Google Patents

Coal liquefaction oil hydrotreating catalyst and preparation method and application thereof Download PDF

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CN108393091B
CN108393091B CN201611052918.6A CN201611052918A CN108393091B CN 108393091 B CN108393091 B CN 108393091B CN 201611052918 A CN201611052918 A CN 201611052918A CN 108393091 B CN108393091 B CN 108393091B
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pore volume
impeller
percent
reactor
volume
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CN108393091A (en
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朱慧红
孙素华
金浩
杨光
杨涛
蒋立敬
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a coal liquefied oil hydrotreating catalyst, which takes alumina as a carrier, VIII group metal and VIB group metal as active metal components, and the weight of the catalyst is taken as a reference, wherein the content of the alumina is 70-84%, the content of the VIII group metal is 1-9 wt% calculated by oxides, and the content of the VIB group metal is 15-30 wt% calculated by oxides. The invention also provides a preparation method and application of the catalyst. By adopting the fluidized bed process and the catalyst, the coal liquefied oil can be used as hydrogen-donating solvent oil after being subjected to hydrotreating.

Description

Coal liquefaction oil hydrotreating catalyst and preparation method and application thereof
Technical Field
The invention relates to a hydrogenation catalyst, a preparation method and application thereof, in particular to a method for processing coal liquefaction oil by adopting a fluidized bed to provide hydrogen-donating solvent oil.
Background
The direct coal liquefaction is completed under high temperature and high pressure, and is an advanced clean coal technology which makes hydrogen element enter molecular structures of coal and derivatives thereof by means of a hydrogen supply solvent and a catalyst, thereby converting the coal into liquid fuel or chemical raw materials. Coal is decomposed by heating and unstable free radical fragments generated are subjected to hydrocracking, so that high molecular coal with a complex structure is converted into a low molecular liquid product (coal liquefied oil) with a high H/C atom ratio and a small amount of gaseous hydrocarbon. The solvent used in the direct coal liquefaction reaction is heavy distillate oil in the product of the direct coal liquefaction process, but the solvent has low hydrogen content, high content of polycyclic aromatic hydrocarbon, high aromatic carbon rate and poor hydrogen supply performance. In order to improve the hydrogen supply capacity, heavy distillate oil is usually subjected to appropriate deep hydrogenation treatment, the content of polycyclic aromatic hydrocarbons in the heavy distillate oil is controlled, and finally the aim of improving the hydrogen supply capacity is achieved. At present, the hydrogen supply capability of the circulating solvent is the strongest when the aromatic carbon rate is 40-45 mol%.
The fluidized bed is adopted for hydrotreating coal liquefaction oil, because the catalyst in the fluidized bed is in a boiling state, bed pressure drop cannot be formed, and meanwhile, the catalyst is added and discharged on line, so that the activity of a reaction system is maintained at a certain level, and stable product quality is maintained. The attrition resistance of the ebullated bed catalyst is an important index, and the attrition resistance of the catalyst is closely related to the properties of the raw materials, so that the development of a catalytic material with good caking property is the key to solve the problem.
CN200610027537.2 a coal liquefaction oil boiling bed hydrogenation process, CN200610027539.1 a coal liquefaction oil boiling bed hydrogenation catalyst carrier and a preparation method thereof, and CN200610027538.7 a coal liquefaction oil boiling bed hydrotreating catalyst and a preparation method thereof, wherein the three patents provide a preparation method of a boiling bed coal liquefaction oil hydrotreating catalyst. At least one catalyst in the hydrogenation catalyst contains a fibrous auxiliary agent, the content of the fibrous auxiliary agent in the catalyst is 3-10 wt%, the fibrous auxiliary agent is one or more of alumina fiber, alumina-silica fiber, carbon fiber, alkali-free glass fiber and boron fiber, the length of the fibrous auxiliary agent is 4-500 micrometers, the preferred length is 4-200 micrometers, the best length is 10-80 micrometers, the diameter is 4-100 micrometers, and the preferred diameter is 4-50 micrometers. In the above patent, the mechanical strength and antiwear performance of the catalyst are improved by adding fiber auxiliary agent, but the cost is higher and the addition amount is larger.
CN201310638434.X discloses a coal liquefied oil hydrogenation catalyst carrier, a catalyst and a preparation method thereof, wherein the carrier comprises 5-60wt% of carbon nanotubes, 32-90wt% of alumina, 0-8wt% of silica and 0-8wt% of titanium dioxide, based on the total weight of the carrier being 100%. The catalyst has higher raw material cost, and the cost is increased in the boiling bed process with larger catalyst consumption, so the catalyst is not suitable for industrial popularization and application.
How to prepare the pseudoboehmite raw material with good caking property and low price is a difficult point for processing coal liquefied oil by a fluidized bed. Pseudo-boehmite generally has three preparation methods in industry: aluminum chloride process, aluminum sulfate process, and carbonization process. The first two methods are liquid-liquid reaction, the carbonization method is gas-liquid reaction, the reaction process is that liquid is filled in a reaction kettle, gas is introduced into the bottom of the reaction kettle for reaction, the process requires that the gas is broken into uniform and tiny bubbles to be beneficial to the reaction, and a product with uniform crystal grains is obtained, so that the distribution requirement on the gas is high, and how to enable the gas to form uniform and tiny bubbles to be in good contact with the liquid is a technical problem which needs to be solved urgently in the field at present.
CN201210409431.4 discloses a method for preparing alumina dry glue by a carbonization method. The method is characterized in that a proper amount of RPE type and/or PEP type nonionic surfactant is added in the gelling process, and the nonionic surfactant has the functions of hole expansion and defoaming, so that the generated bubbles are proper and uniform in size, the solution is uniformly contacted with gas, and the method is favorable for generating the alumina with large pore diameter, large pore volume and reasonable pore distribution. The method eliminates bubbles by adding a chemical reagent, the size of the bubbles in the gas cannot be changed, so that the gas cannot be efficiently utilized, the cost of the chemical reagent is high, and the cost of the final product is also influenced.
CN201110350784.7 discloses an alumina carrier and a preparation method thereof. The alumina carrier is prepared by a carbonization method through reaction in a loop reactor, reaction materials are placed in the loop reactor, and then air and/or inert gas and CO are injected2The mixed gas in the loop reactor makes use of the directional and regular circular flow of the fluid in the loop reactor to ensure that the fluid is fully mixed. The method utilizes the advantage that the circulation reactor is beneficial to gas-liquid mass transfer, but the size of the bubbles is still influenced by the size of the nozzle, and the bubbles still have a contact area with more liquid and less gas, so that the gas-liquid can not be effectively utilized.
CN201210432682.4 discloses a method for preparing high-silicon macroporous amorphous silica-alumina dry gel by a carbonization method. The method utilizes that when the reaction pressure reaches 1.0MPa, the solubility of carbon dioxide is improved by more than 10 times compared with that under normal pressure. Along with the improvement of the solubility of the carbon dioxide, the pH value of a reaction system can be effectively reduced, the environment of neutralization reaction is improved, the improvement of the quality of amorphous silica-alumina products is facilitated, and meanwhile, the utilization rate of the carbon dioxide is greatly improved due to the discharge of a small amount of carbon dioxide. The method only improves the dissolution rate of the carbon dioxide, does not provide the reaction effect of the carbon dioxide gas and the sodium metaaluminate liquid, and the closed container is influenced by pressure control, so that the flow rate of the carbon dioxide is limited.
Cn201110169570.x discloses a reactor and a method for preparing aluminum hydroxide. The reactor adopts a self-absorption stirrer component which mainly comprises a rotor and a stator, wherein the rotor adopts a closed back-bending runner type impeller, the rotor is fixed on a stirring shaft, and a flow guide fin is arranged in the stator. Compared with the prior art, the reactor is adopted for carbonization reaction, and a gas compressor is not needed because gas is self-sucked in the stirring process, so that power and investment are saved; due to the self-priming stirring of the rotor and the guiding effect of the stator, the size of bubbles generated after gas distribution is small, and the gas utilization rate is improved by more than one time. The process is a batch reaction and cannot ensure the stability of each batch of materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a coal liquefaction oil hydrotreating catalyst and a preparation method thereof, in particular to a catalyst suitable for fluidized bed coal liquefaction hydrotreating and a preparation method thereof. The preparation method of the pseudo-boehmite realizes the continuous gas-liquid reaction, does not need aging, has short reaction time and good pseudo-boehmite cohesiveness, and the coal liquefied oil hydrotreating catalyst prepared by the raw material has good wear resistance and good hydrogenation performance, and is particularly suitable for a fluidized bed hydrogenation process.
The invention provides a fluidized bed coal liquefied oil hydrotreating catalyst, which takes alumina as a carrier, VIII group metal and VIB group metal as active metal components, and the weight of the catalyst is taken as a reference, wherein the content of the alumina is 70-84%, the content of the VIII group metal is 1-9 wt% calculated by oxides, and the content of the VIB group metal is 15-30 wt% calculated by oxides, the alumina has the following properties that the pore volume is 0.95-1.20 m L/g, the specific surface area is 290-350 m2The most probable pore diameter is 12.5-14.0 nm, and the pore distribution is as follows: the pore volume of pores with the pore diameter less than 8nm accounts for less than 12 percent of the total pore volume, preferably less than 10 percent of the total pore volume, and the pore volume of pores with the pore diameter of 8-15 nm accounts for 69-83 percent of the total pore volume, preferably 72 percent of the total pore volumePercent to 82 percent, and the pore volume of the pores with the diameter of more than 15nm accounts for 5 to 19 percent of the total pore volume, preferably 8 to 18 percent.
In the fluidized bed coal liquefaction oil hydrotreating catalyst, the VIII group metal is Ni and/or Co, and the VIB group metal is W and/or Mo.
The catalyst of the invention has the following physical and chemical properties: the specific surface area is 160-250 m2The pore volume is 0.30-0.60 m L/g, and pores with the pore diameter of 6-15nm account for 65-85% of the total pore volume, preferably 70-85%.
The invention provides a preparation method of a fluidized bed coal liquefaction oil hydrotreating catalyst, which comprises the following steps:
(1) alkaline aluminate and carbon dioxide gas are used as raw materials, and after reaction is carried out through a reactor, pseudo-boehmite is obtained, wherein the reactor comprises a reactor body, a rotatable impeller is arranged at the lower part in the reactor body, an impeller 2 is connected with a rotating shaft 10, the other end of the rotating shaft 10 extends out of a driving device 10 outside the reactor body 1 and is connected with the driving device, a semi-open impeller cover is arranged above the impeller, namely the lower part of the impeller cover is open, at least three holes are formed in the impeller cover, two holes are respectively used as a carbon dioxide gas feed inlet and an alkaline aluminate solution feed inlet, the other hole is used as a circulating material outlet, a circulating pipe is arranged outside the impeller cover, one end of the circulating pipe is opened at the impeller cover and is used as a circulating material outlet, the other end of the circulating pipe is;
(2) roasting the pseudo-boehmite obtained in the step (1) at 500-750 ℃ for 2-6 hours to obtain an alumina carrier;
(3) and (3) preparing a dipping solution from metal salt containing an active metal component, then loading the dipping solution on the alumina carrier prepared in the step (2), and drying and roasting to obtain the fluidized bed coal liquefied oil hydrotreating catalyst.
In the preparation method, the pseudoboehmite obtained in the step (1) has the following particle size distribution by volume fraction: less than 10% of particles with a particle size of less than 10 μm, 76-90% of particles with a particle size of 10-50 μm, less than 14% of particles with a particle size of more than 50 μm, preferably less than 9% of particles with a particle size of less than 10 μm, 82-90% of particles with a particle size of 10-50 μm, and less than 9% of particles with a particle size of more than 50 μm.
In the preparation method, the most probable particle size of the pseudo-boehmite obtained in the step (1) is 35-45 μm.
In the preparation method, the alumina obtained in the step (2) has the following properties that the pore volume is 0.95-1.20 m L/g, and the specific surface area is 290-350 m2The most probable pore diameter is 12.5-14.0 nm, and the pore distribution is as follows: the pore volume of the pores with the pore diameter of less than 8nm accounts for less than 12 percent of the total pore volume, preferably less than 10 percent of the total pore volume, the pore volume of the pores with the pore diameter of 8-15 nm accounts for 69-83 percent of the total pore volume, preferably 72-82 percent of the total pore volume, and the pore volume of the pores with the pore diameter of more than 15nm accounts for 5-19 percent of the total pore volume, preferably 8-18 percent of the total pore volume.
In the preparation method, in the reactor adopted in the step (1), an atomizing nozzle is arranged at the feed inlet of the alkaline aluminate solution, the pressure of the atomizing nozzle is 0.2-0.5 MPa, and the diameter of the atomizing nozzle is 10-30 mu m.
In the preparation method, the impeller cover in the reactor adopted in the step (1) is hemispherical and covers the top and the outer side of the impeller. The holes on the impeller cover can be uniformly arranged on the impeller cover. More than three feed inlets can be arranged in the holes on the impeller cover and are uniformly arranged on the impeller cover, so that the carbon dioxide gas and the alkaline aluminate solution are uniformly sprayed on the rotating impeller.
In the preparation method of the invention, in the reactor adopted in the step (1), an auxiliary agent inlet can be arranged on the circulating pipe.
In the preparation method, in the reactor adopted in the step (1), the ratio of the distance from the overflow port to the bottom of the reactor to the distance from the impeller to the bottom of the reactor is 1.5-2.5: 1.
in the preparation method of the invention, the preparation method of the pseudo-boehmite in the step (1) specifically comprises the following steps: carbon dioxide gas and alkaline aluminate solution are continuously sprayed into a high-speed rotating impeller from a carbon dioxide gas feed port and an alkaline aluminate solution feed port which are arranged on an impeller cover respectively, slurry generated by reaction falls into a reactor from the periphery of the impeller, part of the generated slurry enters a circulating pipe through an inlet of the circulating pipe, circulating materials are sprayed into the high-speed rotating impeller from a circulating material outlet arranged on the impeller cover, the slurry generated by reaction is continuously discharged from an overflow port at the top of the reactor, the discharged slurry is filtered, washed and dried to obtain the pseudo-boehmite, wherein the reaction temperature is controlled to be 10-30 ℃, the retention time is 10-25 min, the pH value of the slurry discharged from the overflow port is controlled to be 9-11, and the volume ratio of the circulating amount of the slurry to the feeding amount of the alkaline aluminate solution is 2: 1-5: 1. the drying conditions were as follows: drying the mixture for 3 to 6 hours at the temperature of 110 to 130 ℃.
In the preparation method, the method for calculating the retention time comprises the following steps: residence time = reactor volume ÷ (liquid phase feed rate + rate of circulation of the resulting slurry).
In the preparation method, the alkaline aluminate in the step (1) is sodium metaaluminate and/or potassium metaaluminate, preferably sodium metaaluminate; the concentration of the alkaline aluminate solution is 15-55 gAl2O3/L, preferably 20 to 35 gAl2O3L, it can be prepared by conventional preparation method.
In the preparation method of the invention, the carbon dioxide gas in the step (1) can adopt a mixed gas containing carbon dioxide, wherein CO is2The volume fraction of (A) is 30-60%. The mixed gas may contain any of air, nitrogen, and inert gas in addition to carbon dioxide.
In the preparation method of the invention, the drying conditions in the step (3) are as follows: drying at 100-150 ℃ for 2-24 h; the roasting conditions in the step (3) are as follows: the roasting temperature is 400-600 ℃, and the roasting time is 2-8 h.
In the preparation method of the invention, in the preparation process of the pseudo-boehmite in the step (1), an auxiliary agent, such as SiO, can be added according to actual needs2、P2O5、B2O3、TiO2One or more precursors, which are added in the form of water-soluble inorganic substances, can be added together with the alkaline aluminate solution or can be added separately. Auxiliary agentThe precursor can be one or more of silicate, phosphoric acid, boric acid, titanium sulfate and titanium nitrate. The addition amount of the auxiliary agent can be added according to the requirements of the catalyst.
In the preparation method, the active metal component in the step (3) is loaded by a conventional method, namely, a metal salt containing the active metal component is prepared into an impregnation solution, and then the impregnation solution is loaded on a carrier, and the carrier is dried and roasted to obtain the catalyst. The dipping solution containing the active metal component is a Mo-Ni system. The coal liquefaction oil refers to the generated oil obtained by directly liquefying coal, and the properties of the coal liquefaction oil are as follows: the aromatic carbon rate is 0.5-0.65, and the aromatic hydrocarbon content is generally 50-90 wt%.
The invention also relates to a method for applying the catalyst to the coal liquefaction oil boiling bed hydrogenation process, and the applied process conditions are as follows: the reaction pressure is 10-20 MPa, the temperature is 350-400 ℃, and the liquid hourly space velocity is 0.1-2.0 h-1The volume ratio of hydrogen to oil is 100-1000.
The invention adopts a specific reactor, so that alkaline aluminate solution and carbon dioxide gas are broken into fine liquid drops by an impeller rotating at high speed, the carbon dioxide gas reacts on the surface of the fine liquid drops, and a vacuum environment is formed between the impeller and a cover through the high-speed rotation of the impeller, so that part of generated slurry enters a circulating pipe from a circulating material inlet at the bottom of the reactor and is sprayed onto the impeller rotating at high speed through a circulating material outlet, and meanwhile, the circulating material amount and proper reaction conditions are controlled, so that the generated aluminum hydroxide crystal grains are fine and uniform, the cohesiveness of aluminum oxide is good, and the prepared coal liquefied oil hydrotreating catalyst has good wear resistance and good hydrogenation performance.
The method has simple preparation process, realizes the continuous gas-liquid reaction, does not need aging, has short reaction time and stable properties of the alumina product. In addition, the alkaline aluminate and the carbon dioxide are used as raw materials, so that the cost is low, the raw materials are easy to obtain, and the large-scale production is facilitated.
Drawings
FIG. 1 is a schematic view of the structure of a reactor used in the present invention.
Detailed Description
The reactor structure used by the invention is shown in figure 1, the reactor comprises a reactor body 1, a rotatable impeller 2 is arranged at the lower part in the reactor body 1, the impeller 2 is connected with a rotating shaft 10, the other end of the rotating shaft 10 extends out of a driving device 10 outside the reactor body 1 and is connected with the driving device, a semi-open impeller cover 3 is arranged above the impeller 2, namely the lower part of the impeller cover 3 is open, at least three holes are arranged on the impeller cover 3, two holes 4 and 5 are respectively used as a carbon dioxide gas feeding hole and an alkaline aluminate solution feeding hole, the other hole 6 is used as a circulating material outlet, a circulating pipe 7 is arranged outside the impeller cover 3, one end of the circulating pipe 7 is opened at the impeller cover to be used as a circulating material outlet, the other end of the circulating pipe is opened at the bottom. The circulation pipe may be provided with an auxiliary inlet 9.
The preparation process of the pseudoboehmite comprises the following steps: the method comprises the following steps of continuously spraying carbon dioxide mixed gas and alkaline aluminate solution onto an impeller 2 rotating at a high speed from a carbon dioxide gas feed port 4 and an alkaline aluminate solution feed port 5 which are arranged on an impeller cover respectively, enabling part of generated slurry to enter a circulating pipe 7 through a circulating material inlet at one end of the circulating pipe, spraying the circulating material onto the impeller 2 rotating at a high speed from a circulating material outlet 6 which is arranged on the impeller cover 3, continuously discharging the slurry generated by reaction from an overflow port 8 at the top of the reactor, filtering, washing and drying the discharged slurry to obtain the pseudoboehmite, wherein the reaction temperature is controlled to be 10-30 ℃, the retention time is 10-25 min, the pH value of the slurry discharged from the overflow port is controlled to be 9-11, and the volume ratio of the circulating amount of the slurry to the alkaline aluminate solution feed amount is 2: 1-5: 1.
the technical solution of the present invention is further illustrated by the following examples, but is not limited to the following examples. In the present invention, the particle size is measured by a laser particle sizer. In the present invention, the pore volume, pore distribution and specific surface area are measured by a low temperature liquid nitrogen adsorption method. The trihydrate content was determined with an X-ray diffractometer.
Example 1
(1) Preparation of pseudo-boehmite
Preparing 360 gAl of industrial first-grade aluminum hydroxide powder and industrial first-grade sodium hydroxide2O3Concentrated sodium metaaluminate solution of/L, then diluted to 25 gAl concentration2O3L continuous spraying carbon dioxide gas mixture and diluted sodium metaaluminate solution into impeller 2 rotating at high speed from inlet 4 and 5 on impeller cover, allowing the resultant slurry to fall into the reactor from the periphery of impeller 2, allowing part of the resultant slurry to enter circulating pipe 7 via circulating material inlet, spraying the circulating material onto impeller 2 rotating at high speed from circulating material outlet 6 on impeller cover 3, continuously discharging the resultant slurry from overflow port 8 on the top of the reactor, filtering, washing, and drying to obtain pseudoboehmite, wherein CO in the gas mixture2Is 50% by volume, the remainder being air gas. The pressure of an atomizing nozzle is 0.5MPa, the diameter of the atomizing nozzle is 30 mu m, the reaction temperature is controlled to be 20 ℃, the retention time is 15min, the pH value of the slurry discharged from an overflow port is controlled to be 10, and the volume ratio of the circulation volume of the slurry to the feeding volume of the sodium metaaluminate solution is 3: 1. taking filtered samples in the reaction time of 1h and the reaction time of 5h respectively, and drying the samples at the drying temperature of 120 ℃ for 4h to obtain pseudo-boehmite Al0-1 and Al 0-5.
(2) Catalyst preparation
And (2) adding 2.8g of sesbania powder into 200g of the prepared Al0-5 pseudo-boehmite raw material, balling and forming, and roasting the balling sample at 650 ℃ for 5 hours to obtain a carrier Z-1 with the particle size of 0.4-0.8 mm.
32.50g of phosphoric acid is weighed, 450m L of distilled water is added, 94.60g of molybdenum oxide and 40.46g of basic nickel carbonate are sequentially added, the mixture is heated and stirred until the molybdenum oxide and the basic nickel carbonate are completely dissolved, the solution is fixed to the volume of 500m L by using the distilled water, solution L-1 is obtained, carrier Z-1 is saturated and impregnated by using solution L-1, the carrier Z-1 is dried at 110 ℃ for 2h, and the carrier Z-1 is roasted at 550 ℃ for 5h, so that the catalyst C-1 is obtained.
Example 2
The other conditions were the same as in example 1 except that the nozzle diameter was changed to 20 μm and the mixed gas CO was changed270% by volume, the remainder being air gas. pH value of slurry at overflow portAt 10.5, a sample obtained after 1 hour of reaction was taken to obtain pseudo-boehmite Al0-2, a carrier Z-2 and a catalyst C-2.
Example 3
(1) Preparation of pseudo-boehmite
The other conditions were the same as in example 1 except that the volume ratio of the circulating amount of the slurry to the feeding amount of the sodium metaaluminate solution was changed to 5: 1, and ammonium dihydrogen phosphate having a molar concentration of 1.02 mol/L was added to obtain a sample after 1 hour of the reaction, thereby obtaining pseudo-boehmite Al 0-3.
(2) Preparation of the catalyst
Taking 200g of prepared Al0-3 pseudo-boehmite raw material, adding 2.8g of sesbania powder and 25g of ammonia water, balling and forming, and roasting the balling sample at 550 ℃ for 3h to obtain a carrier Z-3 with the particle size of 0.4-0.8 mm.
37.49g of phosphoric acid is weighed, 450m L of distilled water is added, 135.77g of molybdenum oxide and 51.02g of basic nickel carbonate are sequentially added, the mixture is heated and stirred until the molybdenum oxide and the basic nickel carbonate are completely dissolved, the solution is subjected to constant volume to 500m L by using the distilled water, solution L-2 is obtained, carrier Z-3 is saturated and impregnated by using L-2 solution, the carrier Z-3 is dried at 110 ℃ for 4h, and the carrier Z-3 is roasted at 500 ℃ for 3h, so that the catalyst C-3 is obtained.
Example 4
(1) Preparation of pseudo-boehmite
Preparing 360 gAl of industrial first-grade aluminum hydroxide powder and industrial first-grade sodium hydroxide2O3Concentrated sodium metaaluminate solution of/L, then diluted to 50 gAl concentration2O3L spraying carbon dioxide gas mixture and diluted sodium metaaluminate solution into impeller 2 rotating at high speed from inlet 4 and 5 on impeller cover, allowing the resultant slurry to fall into the reactor from the periphery of impeller 2, allowing part of the resultant slurry to enter into circulation pipe 7 via circulation material inlet at one end of circulation pipe, spraying the circulation material onto impeller 2 rotating at high speed from circulation material outlet 6 on impeller cover 3, discharging the resultant slurry from overflow port 8 at the top of the reactor, filtering, washing, and drying to obtain pseudo-boehmite, wherein the CO in the gas mixture is in the form of pseudo-boehmite2The volume fraction of (a) is 60%, and the balance is nitrogen gas. The pressure of the atomizing nozzle is 0.4MPa, and the atomizing nozzleThe diameter is 15 mu m, the reaction temperature is controlled to be 15 ℃, the retention time is 20min, the pH value of the slurry discharged from the overflow port is controlled to be 11, and the volume ratio of the circulating amount of the slurry to the feeding amount of the sodium metaaluminate solution is 4: 1. and (3) taking a sample after reaction for 1h, filtering, and drying at the drying temperature of 110 ℃ for 6 h to obtain the pseudo-boehmite Al 0-4.
(2) Preparation of the catalyst
Taking 200g of prepared Al0-4 pseudo-boehmite raw material, adding 2.8g of methyl fiber, balling and forming, and roasting the balling sample at 500 ℃ for 3h to obtain a carrier Z-4 with the granularity of 0.4-0.8 mm.
Saturating and impregnating the carrier Z-4 with solution L-2, drying at 110 ℃ for 4h, and roasting at 480 ℃ for 3h to obtain the catalyst C-4.
Comparative example 1
(1) Preparation of pseudo-boehmite
Prepared according to the method disclosed in CN 201110350784.7. Preparing 365 gAl by industrial primary aluminum hydroxide powder and industrial primary sodium hydroxide2O3Concentrated sodium metaaluminate solution of/L, then diluted to 25 gAl concentration2O33L of sodium metaaluminate solution of/L is added into a loop reactor, the gelling temperature is controlled to be 20 ℃, organic pore-expanding agent alkylphenol and ethylene oxide condensation compound (OP-10) and polyoxyethylene sorbitan monooleate (T-80) are added, wherein the weight ratio of OP-10 to T-80 is 60: 40, the dosage of the organic pore-expanding agent accounts for 0.6 percent of the weight of the sodium metaaluminate, diesel oil is taken as a defoaming agent, the dosage of the defoaming agent accounts for 0.5 percent of the weight of the organic pore-expanding agent, air and CO are introduced into the loop reactor2The flow rate of the mixed gas of (1) is 8m L/min, wherein CO2Is 50 percent, is stirred by mixed gas, and stops gelling when the pH value is reduced to 10. The slurry was washed with 40 ℃ hot water to neutrality and dried at 120 ℃ for 4 hours to obtain pseudo-boehmite F0-1.
(2) Catalyst preparation
And (2) adding 2.8g of sesbania powder into 200g of the prepared F0-1 pseudo-boehmite raw material, balling and forming, and roasting the balling sample at 650 ℃ for 5 hours to obtain the carrier F-1 with the granularity of 0.4-0.8 mm.
Saturating and soaking the carrier F-1 with solution L-1, drying at 110 ℃ for 2h, and roasting at 550 ℃ for 5h to obtain the catalyst C-F-1.
Comparative example 2
The reactor adopted in the embodiment 1 is not provided with a circulating pipe 7 and a circulating material outlet 6 arranged on an impeller cover, and the specific process is as follows: preparing 360 gAl of industrial first-grade aluminum hydroxide powder and industrial first-grade sodium hydroxide2O3Concentrated sodium metaaluminate solution of/L, then diluted to 25 gAl concentration2O3L continuous spraying carbon dioxide gas mixture and diluted sodium metaaluminate solution into impeller 2 rotating at high speed from inlet 4 and 5 on impeller cover, allowing the resultant slurry to fall into reactor via impeller 2, discharging the resultant slurry from overflow port 8 at top of reactor, filtering, washing, and drying to obtain pseudoboehmite, wherein CO in the gas mixture2The volume fraction of the slurry is 50 percent, the nozzle pressure of an atomizing nozzle at a liquid phase feed inlet is 0.5MPa, the diameter of the nozzle is 30 mu m, the reaction temperature is controlled to be 20 ℃, the retention time is 15min, and the pH value of the slurry discharged from an overflow port is controlled to be 10. Taking a sample after reaction for 1h, filtering, and drying at the drying temperature of 120 ℃ for 4h to obtain the pseudoboehmite F0-2.
(2) Catalyst preparation
And (2) adding 2.8g of sesbania powder into 200g of prepared F0-2 pseudo-boehmite raw material, balling and forming, and roasting the balling sample at 650 ℃ for 5 hours to obtain the carrier F-2 with the granularity of 0.4-0.8 mm.
Saturating and soaking the carrier F-2 with solution L-1, drying at 110 ℃ for 2h, and roasting at 550 ℃ for 5h to obtain the catalyst C-F-2.
Comparative example 3
Preparing 360 gAl of industrial first-grade aluminum hydroxide powder and industrial first-grade sodium hydroxide2O3Concentrated sodium metaaluminate solution of/L, then diluted to 25 gAl concentration2O3L spraying carbon dioxide gas mixture and diluted sodium metaaluminate solution into impeller 2 via inlets 4 and 5 on impeller cover, allowing the resultant slurry to fall into reactor via impeller 2, and collecting the partial slurryThe recycled materials enter a recycling pipe 7 through a recycling material inlet at one end of the recycling pipe, the recycling materials are sprayed onto an impeller 2 rotating at a high speed from a recycling material outlet 6 arranged on an impeller cover 3, slurry generated by reaction is continuously discharged from an overflow port 8 at the top of the reactor, and the discharged slurry is filtered, washed and dried to obtain the pseudo-boehmite. Wherein CO is contained in the mixed gas2The volume fraction of the slurry is 50 percent, the nozzle pressure of an atomizing nozzle of a liquid phase feed port is 0.5MPa, the diameter of the nozzle is 30 mu m, the reaction temperature is controlled to be 20 ℃, the retention time is 40min, the pH value of the slurry discharged from an overflow port is controlled to be 10, and the volume ratio of the circulation quantity of the slurry to the feeding quantity of the sodium metaaluminate solution is 3: 1. taking a sample after reaction for 1h, filtering, and drying at the drying temperature of 120 ℃ for 4h to obtain the pseudoboehmite F0-3.
(2) Catalyst preparation
And (2) adding 2.8g of sesbania powder into 200g of the prepared F0-3 pseudo-boehmite raw material, balling and forming, and roasting the balling sample at 650 ℃ for 5 hours to obtain the carrier F-3 with the granularity of 0.4-0.8 mm.
Saturating and soaking the carrier F-3 with solution L-1, drying at 110 ℃ for 2h, and roasting at 550 ℃ for 5h to obtain the catalyst C-F-3.
The properties of the pseudo-boehmite obtained above are shown in Table 1, and the properties of the catalyst are shown in Table 2. .
TABLE 1 Properties of pseudo-boehmite
Numbering Al0-1-1 Al0-1-5 Al0-2 Al0-3 Al0-4 F0-1 F0-2 F0-3
Particle size distribution (volume)%
<10μm 8.1 7.8 6.6 7.6 9.0 25.3 20.1 10.5
10～50μm 82.9 83.3 86.9 83.7 84.8 53.6 60.4 73.9
>50μm 9.0 8.9 6.5 8.7 6.2 21.1 19.5 15.6
Most probable particle diameter, μm 41.1 40.9 42.6 38.7 37.3 30.5 32.4 31.7
The content of trihydrate in wt% <1% <1% <1% <1% <1% <1% <1% 5%
TABLE 2 physicochemical Properties of the catalyst
Numbering C-1 C-2 C-3 C-4 C-F-1 C-F-2 C-F-3
Specific surface area, m2/g 219 201 195 210 241 229 176
Pore volume, m L/g 0.61 0.60 0.59 0.62 0.52 0.54 0.42
Abrasion index, wt.% 0.58 0.61 0.55 0.50 1.24 1.03 3.18
Catalyst composition in wt%
MoO3 14.21 14.32 19.34 19.28 14.35 14.41 14.19
NiO 3.41 3.38 3.89 3.91 3.47 3.51 3.43
P 1.26 1.19 1.37 1.34 1.21 1.32 1.25
The prepared fluidized bed coal liquefaction oil hydrogenation catalyst is loaded on a 4L fluidized bed device for activity evaluation, the properties and evaluation conditions of the used raw oil are shown in table 3, and the evaluation conditions are shown in table 4.
TABLE 3 Properties and evaluation conditions of the stock oils
Item Numerical value
Properties of crude oil
Sulfur, wt.% 0.28
Total aromatic hydrocarbons,% 72.3
Aromatic carbon content, mol% 64.02
Process conditions
Reaction temperature/. degree.C 360
Reaction pressure/MPa 12
Space velocity/h-1 1.5
Volume ratio of hydrogen to oil 600：1
TABLE 4 evaluation results of catalysts
Numbering C-1 C-2 C-3 C-4 C-F-1 C-F-2 C-F-3
Generating oily substance
Sulfur, ng/. mu.l 14.4 13.8 6.3 5.6 35.6 31.2 32.1
Total aromatic hydrocarbons,% 64.3 62.5 58.9 57.4 66.1 65.4 66.4
Aromatic carbon content, mol% 42.82 42.64 40.01 39.43 50.81 49.14 51.82
As can be seen from the data in the table: the pseudo-boehmite prepared by the method has centralized particle size distribution, less water content and stable product property, the hydrotreating catalyst for the coal liquefaction oil in the boiling bed prepared by the method has good wear resistance and good hydrogenation performance, the content of aromatic hydrocarbon of the coal liquefaction oil after hydrotreating in the boiling bed is reduced, the aromatic hydrocarbon rate is reduced, and the pseudo-boehmite can be used as hydrogen-supplying solvent oil of a coal liquefaction unit.

Claims (30)

1. A fluidized bed coal liquefied oil hydrotreating catalyst takes alumina as a carrier, VIII group metal and VIB group metal as active metal components, and the catalyst takes the weight of the catalyst as a reference, wherein the content of the alumina is 70-84%, the content of the VIII group metal is 1-9 wt% calculated by oxides, and the content of the VIB group metal is 15-30 wt% calculated by oxides, and the alumina has the following properties that the pore volume is 0.95-1.20 m L/g, the specific surface area is 290-350 m2The most probable pore diameter is 12.5-14.0 nm, and the pore distribution is as follows: the pore volume of pores with the pore diameter less than 8nm accounts for less than 12 percent of the total pore volume, the pore volume of pores with the pore diameter of 8-15 nm accounts for 69-83 percent of the total pore volume, and the pore volume of pores with the pore diameter more than 15nm accounts for 5-19 percent of the total pore volume.
2. The ebullated-bed coal liquefied oil hydrotreating catalyst according to claim 1, characterized in that: the pore volume of pores with the pore diameter less than 8nm accounts for less than 10 percent of the total pore volume, the pore volume of pores with the pore diameter of 8-15 nm accounts for 72-82 percent of the total pore volume, and the pore volume of pores with the pore diameter more than 15nm accounts for 8-18 percent of the total pore volume.
3. The ebullated-bed coal liquefied oil hydrotreating catalyst according to claim 1, characterized in that: the VIII group metal is Ni and/or Co, and the VIB group metal is W and/or Mo.
4. The ebullated-bed coal liquefied oil hydrotreating catalyst according to claim 1, characterized in that: the specific surface area of the catalyst is 160-250 m2The pore volume is 0.30-0.60 m L/g, and pores with the pore diameter of 6-15nm account for 65-85% of the total pore volume.
5. The ebullated-bed coal liquefied oil hydrotreating catalyst according to claim 1, characterized in that: the pore diameter of the catalyst is 6-15nm, and accounts for 70-85% of the total pore volume.
6. The method for preparing the catalyst for hydrotreating of liquefied oil of fluidized bed coal according to any of claims 1 to 5, characterized in that: the preparation method comprises the following steps:
(1) alkaline aluminate and carbon dioxide gas are used as raw materials, and after reaction is carried out through a reactor, pseudo-boehmite is obtained, wherein the reactor comprises a reactor body, a rotatable impeller is arranged at the lower part in the reactor body, an impeller 2 is connected with a rotating shaft 10, the other end of the rotating shaft 10 extends out of a driving device 10 outside the reactor body 1 and is connected with the driving device, a semi-open impeller cover is arranged above the impeller, namely the lower part of the impeller cover is open, at least three holes are formed in the impeller cover, two holes are respectively used as a carbon dioxide gas feed inlet and an alkaline aluminate solution feed inlet, the other hole is used as a circulating material outlet, a circulating pipe is arranged outside the impeller cover, one end of the circulating pipe is opened at the impeller cover and is used as a circulating material outlet, the other end of the circulating pipe is;
(2) roasting the pseudo-boehmite obtained in the step (1) at 500-750 ℃ for 2-6 hours to obtain an alumina carrier;
(3) and (3) preparing a dipping solution from metal salt containing an active metal component, then loading the dipping solution on the alumina carrier prepared in the step (2), and drying and roasting to obtain the fluidized bed coal liquefied oil hydrotreating catalyst.
7. The method of claim 6, wherein: the pseudoboehmite obtained in the step (1) has the following particle size distribution by volume fraction: the content of particles with the particle size of less than 10 mu m is less than 10 percent, the content of particles with the particle size of 10-50 mu m is 76-90 percent, and the content of particles with the particle size of more than 50 mu m is less than 14 percent.
8. The production method according to claim 6 or 7, characterized in that: the pseudoboehmite obtained in the step (1) has the following particle size distribution by volume fraction: less than 9% of particles with the particle size of less than 10 microns, 82% -90% of particles with the particle size of 10-50 microns, and less than 9% of particles with the particle size of more than 50 microns.
9. The method of claim 6, wherein: the particle size of the pseudo-boehmite obtained in the step (1) is 35-45 μm.
10. The method according to claim 6, wherein the alumina obtained in the step (2) has a pore volume of 0.95 to 1.20m L/g and a specific surface area of 290 to 350m2The most probable pore diameter is 12.5-14.0 nm, and the pore distribution is as follows: the pore volume of pores with the pore diameter less than 8nm accounts for less than 12 percent of the total pore volume, the pore volume of pores with the pore diameter of 8-15 nm accounts for 69-83 percent of the total pore volume, and the pore volume of pores with the pore diameter more than 15nm accounts for 5-19 percent of the total pore volume.
11. The method according to claim 6 or 10, wherein the alumina obtained in the step (2) has a pore volume of 0.95 to 1.20m L/g and a specific surface area of 290 to 350m2The most probable pore diameter is 12.5-14.0 nm, and the pore distribution is as follows: the pore volume of the pores with the pore diameter less than 8nm accounts for less than 10 percent of the total pore volume, the pore volume of the pores with the pore diameter of 8-15 nm accounts for 72-82 percent of the total pore volume,the pore volume of the pores with the diameter larger than 15nm accounts for 8 to 18 percent of the total pore volume.
12. The method of claim 6, wherein: in the reactor adopted in the step (1), an atomizing nozzle is arranged at the feed inlet of the alkaline aluminate solution, the pressure of the atomizing nozzle is 0.2-0.5 MPa, and the diameter of the atomizing nozzle is 10-30 mu m.
13. The method of claim 6, wherein: and (2) in the reactor adopted in the step (1), the impeller cover is hemispherical and covers the top and the outer side of the impeller.
14. The method of claim 6, wherein: the holes on the impeller cover are uniformly arranged on the impeller cover.
15. The method of claim 6, wherein: in the reactor adopted in the step (1), an auxiliary agent inlet is arranged on the circulating pipe.
16. The method of claim 6, wherein: in the reactor adopted in the step (1), the ratio of the distance from the overflow port to the bottom of the reactor to the distance from the impeller to the bottom of the reactor is 1.5-2.5: 1.
17. the method of claim 6, wherein: the preparation method of the pseudoboehmite in the step (1) comprises the following steps: carbon dioxide gas and alkaline aluminate solution are respectively continuously sprayed into the impeller rotating at high speed from a carbon dioxide gas feed port and an alkaline aluminate solution feed port which are arranged on the impeller cover, slurry generated by the reaction falls into the reactor from the periphery of the impeller, part of the generated slurry enters the circulating pipe through the inlet of the circulating pipe, circulating materials are sprayed into the impeller rotating at high speed from the circulating material outlet which is arranged on the impeller cover, the slurry generated by the reaction is continuously discharged from the overflow port at the top of the reactor, and the discharged slurry is filtered, washed and dried to obtain the pseudo-boehmite.
18. The method of claim 17, wherein: in the preparation process of the pseudo-boehmite, the reaction temperature is 10-30 ℃, the retention time is 10-25 min, the pH value of slurry discharged from an overflow port is controlled to be 9-11, and the volume ratio of the circulation volume of the slurry to the feeding volume of an alkaline aluminate solution is 2: 1-5: 1.
19. the method of claim 17, wherein: the drying conditions were as follows: drying the mixture for 3 to 6 hours at the temperature of 110 to 130 ℃.
20. The method of claim 6, wherein: the alkaline aluminate in the step (1) is sodium metaaluminate and/or potassium metaaluminate, and the concentration of the alkaline aluminate solution is 15-55 gAl2O3/L。
21. The method of claim 6, wherein: the alkaline aluminate in the step (1) is sodium metaaluminate; the concentration of the alkaline aluminate solution is 20-35 gAl2O3/L。
22. The method of claim 6, wherein: the carbon dioxide gas in the step (1) adopts mixed gas containing carbon dioxide, wherein CO2The volume fraction of (A) is 30-60%.
23. The method of claim 22, wherein: the carbon dioxide mixed gas contains any one of air, nitrogen and inert gas in addition to carbon dioxide.
24. The method of claim 6, wherein: the drying conditions in step (3) are as follows: drying at 100-150 ℃ for 2-24 h; the roasting conditions in the step (3) are as follows: the roasting temperature is 400-600 ℃, and the roasting time is 2-8 h.
25. The method of claim 6, wherein: adding an auxiliary agent in the preparation process of the pseudo-boehmite in the step (1), wherein the auxiliary agent is SiO2、P2O5、B2O3、TiO2One or more of the above precursors.
26. The method of claim 25, wherein: the precursor is added in the form of a water-soluble inorganic substance, together with an alkaline aluminate solution, or separately.
27. The method of claim 25, wherein: the auxiliary agent precursor is one or more of silicate, phosphoric acid, boric acid, titanium sulfate and titanium nitrate.
28. Use of a catalyst according to any one of claims 1 to 5 in the hydroprocessing of coal-to-liquid oil boiling beds.
29. Use according to claim 28, wherein: the coal liquefaction oil refers to the generated oil obtained by directly liquefying coal, and has the following properties: the aromatic carbon rate is 0.5-0.65, and the aromatic hydrocarbon content is 50-90 wt%.
30. Use according to claim 28, wherein: the process conditions of the fluidized bed are as follows: the reaction pressure is 10-20 MPa, the temperature is 350-400 ℃, and the liquid hourly space velocity is 0.1-2.0 h-1The volume ratio of hydrogen to oil is 100-1000.
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