CN116060023A - Hydrogenation catalyst and preparation method thereof - Google Patents

Hydrogenation catalyst and preparation method thereof Download PDF

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CN116060023A
CN116060023A CN202111269085.XA CN202111269085A CN116060023A CN 116060023 A CN116060023 A CN 116060023A CN 202111269085 A CN202111269085 A CN 202111269085A CN 116060023 A CN116060023 A CN 116060023A
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solution
reaction kettle
reaction
hydrogenation
catalyst
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CN116060023B (en
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吕振辉
朱慧红
金浩
杨光
刘璐
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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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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

Abstract

The invention discloses a hydrogenation catalyst and a preparation method thereof. The catalyst comprises alumina and hydrogenation active metal components, and has the following properties: the pore volume is 1.3-1.5 mL/g; specific surface area of 200-350 m 2 The pore size of the polymer/g may be less than or equal to 100nm, preferably 160 to 210nm. The method comprises the following steps: (1) Adding an organic solvent, a polar metal seed crystal, an acidic solution I and an alkaline solution I into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I; (2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II; (3) The sol II and the acid solution II or the alkaline solution II flow into a second reaction kettle in parallel to be neutralized and gel to obtain a generated liquid III; (4) The generated liquid III enters an aging kettle for aging; (5) Drying and roasting the ageing material obtained in the step (4) to obtain the hydrogenation catalyst; wherein the alumina and the hydrogenation active metal are introduced into the hydrogenation catalyst from an acidic solution and/or a basic solution. The hydrogenation catalyst has the characteristics of large particle size, concentrated distribution, high specific surface area, large pore volume, large pore diameter and the like, and can be used as a hydrogenation catalyst for poor raw materials.

Description

Hydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to the field of catalyst preparation, in particular to a method for continuously producing hydrogenation catalysts.
Background
At present, the production mode of pseudo-boehmite mainly comprises an inorganic aluminum salt method and an organic aluminum salt method, and batch kettle reactors are adopted in the production process. Pseudo-boehmite is mainly prepared by a precipitation mechanism, wherein precipitation refers to a process of generating insoluble substances through chemical reaction in a liquid phase and forming a new solid phase to be settled out of the liquid phase. From classical theoretical analysis of precipitation, the precipitate formation process is divided into: (1) nucleation: because of the continuous collision motion of molecules or ions, the molecules in the local area are clustered, the aggregation is not only due to the collision among moving particles in the solution, but also the mutual adhesion of the moving particles through weak acting force (Van der Waals force), chemical bonds are generated through crystals, and the aggregation is solidified; (2) Crystal nucleus growth: cluster molecular particles are contacted with each other and combined to grow; wherein, the colloid is uniform, the particles are tiny, and the method has very strong effect on nucleation and crystal growth.
The coprecipitation method is a typical method for preparing aluminum hydroxide. The method is to prepare aluminum salt from raw materials by taking water as a medium, and then to control certain solution concentration, solution flow rate, temperature and reaction time, and to prepare the aluminum hydroxide by acid/alkali neutralization. However, the initial nuclei Al (OH) in the coprecipitation process 3 The polymer has complex structure, small molecular polarity and extremely small solubility, so that the aggregation rate is far higher than the orientation rate, and amorphous gelatinous precipitation is easy to generate, so that the polymer has low crystallinity, incomplete crystal form and unsatisfactory pore structure. Accordingly, the same problems exist with catalysts prepared by the coprecipitation method.
CN103787390a discloses a preparation method of pseudo-boehmite, comprising the following steps: (1) Performing gel forming reaction on the acidic aluminum salt solution and the alkaline solution, and then aging; the glue forming reaction and aging are carried out under the condition of ultrasonic radiation, ultrasonic waves with different frequencies are adopted in the glue forming reaction process and the aging process, and ultrasonic waves with the frequency of 10-160 kHz are adopted in the glue forming reaction process; the aging process adopts ultrasonic frequency which is 1-50 kHz higher than that of the gel forming reaction process; (2) filtering and washing the aged materials; (3) And (3) drying the material obtained in the step (2) to obtain pseudo-boehmite. The method is to prepare pseudo-boehmite by controlling the grain size by using ultrasonic waves with different frequencies during the gelling and aging.
CN101890379a discloses a bulk catalyst and a process for preparing the same. The bulk phase catalyst is obtained by respectively obtaining inorganic oxide precursor hydroxide gel and active metal hydroxide gel as raw materials, molding and roasting. In the preparation process of the bulk phase catalyst, as the hydroxide gel contains a surfactant and a hydrocarbon component, nano oxide particles formed after the polymerized hydroxide is dehydrated still have a rod-shaped basic structure and are randomly stacked into a framework structure after being molded and baked.
In the prior art, although the grain size is controlled by different methods so as to prepare hydrogenation catalysts with different pore structures and properties, how to prepare macroporous hydrogenation catalysts with concentrated high specific surface area grain size distribution is an important subject in the field of continuous and intensive research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation catalyst and a preparation method thereof, in particular to a method for continuously producing a macroporous hydrogenation catalyst. The hydrogenation catalyst has the characteristics of large particle size, concentrated distribution, high specific surface area, large pore volume, large pore diameter and the like, and can be used as a hydrogenation catalyst for poor raw materials.
The first aspect of the invention provides a hydrogenation catalyst comprising alumina and a hydrogenation-active metal component, which is characterized by the following: the pore volume is 1.3-1.5 mL/g; specific surface area of 200-350 m 2 The pore size of the polymer/g may be less than or equal to 100nm, preferably 160 to 210nm.
In the hydrogenation catalyst of the invention, the particle size distribution of the catalyst is as follows: the proportion of the crystal grains with the grain diameter smaller than 200 mu m is 0.5% -5.0%, the proportion of the crystal grains with the grain diameter of 200-350 mu m is 2.0% -5.0%, and the proportion of the crystal grains with the grain diameter larger than 350 mu m is 90.0% -95.0%.
In the hydrogenation catalyst of the invention, the hydrogenation active metal is at least one metal selected from the group consisting of group VIB and group VIII metals. The group VIB metal is at least one selected from Mo and W. The VIII group metal is selected from at least one of Ni and Co.
In the hydrogenation catalyst of the present invention, the mass content of the hydrogenation active metal in terms of oxide is 10% to 80%, preferably 40% to 70%, and the mass content of alumina is 20% to 90%, preferably 30% to 60%, based on the mass of the catalyst.
In the hydrogenation catalyst of the present invention, preferably, the mass content of the group VIB metal in terms of oxide is 5% to 70%, preferably 35% to 65%, the mass content of the group VIII metal in terms of oxide is 5% to 50%, preferably 5% to 30%, and the mass content of the alumina is 20% to 90%, preferably 30% to 60%, based on the mass of the catalyst.
The second aspect of the invention provides a method for preparing a hydrogenation catalyst, comprising:
(1) Adding an organic solvent, a polar metal seed crystal, an acidic solution I and an alkaline solution I into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II;
(3) The sol II and the acid solution II or the alkaline solution II flow into a second reaction kettle in parallel to be neutralized and gel to obtain a generated liquid III;
(4) The generated liquid III enters an aging kettle for aging;
(5) Drying and roasting the ageing material obtained in the step (4) to obtain the hydrogenation catalyst;
wherein, the components of the acid solution I and the alkaline solution I introduced into the hydrogenation catalyst comprise alumina and hydrogenation active metals, namely first alumina and first hydrogenation active metals, and the components of the acid solution II or the alkaline solution II introduced into the hydrogenation catalyst comprise alumina and hydrogenation active metals, namely second alumina and second hydrogenation active metals.
The preparation method of the hydrogenation catalyst is preferably carried out in a continuous mode, wherein a plurality of settling tanks used in the step (2) and a plurality of ageing tanks used in the step (4) can be arranged, and the continuous production is switched.
In the method of the invention, when the hydrogenation catalyst is continuously prepared, preferably, the first reaction kettle in the step (1) is operated in a mode of discharging the generated liquid I out of the first reaction kettle in an overflow mode. When the first reaction kettle is started, preferably, an organic solvent and a polar metal seed crystal are firstly added as base solution, and then an acidic solution I and an alkaline solution I are added in parallel flow for neutralization and gel formation until the generated solution I starts to be discharged out of the first reaction kettle. Wherein the addition amount of the organic solvent in the base solution is 1/5-1/3 of the actual effective use volume of the first reaction kettle, when the generated solution I is discharged out of the first reaction kettle, the acidic solution I and the alkaline solution I in the first reaction kettle are prepared by using Al 2 O 3 And the addition amount of the polar metal salt seed crystal is 0.1-5.0%, preferably 0.2-2.0% based on the total mass of the hydrogenation active metal oxide.
In the method of the invention, when the hydrogenation catalyst is continuously prepared, preferably, the second reaction kettle in the step (3) adopts an overflow type operation mode for discharging the generated liquid III out of the second reaction kettle. When the second reaction kettle is started, preferably, the bottom water is added first, then the sol II and the acid solution II or the alkaline solution II are added in parallel flow for neutralization and gel formation, and the generated liquid III starts to be discharged from the second reaction kettle. Wherein, the addition amount of the bottom water is 1/7-1/2, preferably 1/6-1/3 of the actual effective use volume of the second reaction kettle.
In the method of the present invention, the organic solvent in the step (1) is an organic substance that is not or slightly soluble in water, and the organic substance may be one or more of alkane, alkene, organic alcohol, organic acid, etc., preferably, the carbon number of the organic substance is 5-12.Wherein the molecular structural formula of alkane is C n H 2n+2 (n is more than or equal to 5, preferably n=5-12), and at least one of pentane, hexane, dodecane and the like can be selected; the molecular structural formula of the olefin is C n H 2n (n is more than or equal to 5, preferably n=5-12), and at least one of pentene, hexene and the like can be selected; the organic alcohol is at least one selected from organic monohydric alcohol and organic polyalcohol, wherein the molecular structural formula of the organic monohydric alcohol is C n H 2n+2 O (n is more than or equal to 6, preferably n=6-12), and at least one of n-hexanol, n-heptanol and the like can be selected; wherein the molecular structural formula of the polyol is C n H 2n+2-x (OH) x (n is more than or equal to 6, preferably n=6-12, and x is more than or equal to 3), and at least one of polyhydric alcohols such as pentaerythritol, glycerol, trimethylolethane, xylitol, sorbitol and the like can be selected; the organic acid may be at least one of aliphatic or aromatic carboxylic acid, such as benzoic acid.
In the method of the invention, the polar metal seed crystal is selected from metal halogen compounds, and at least one of metal sulfides is preferably one or more of AgCl, znS, cuS or HgS.
In the method of the invention, the operation conditions of the first reaction kettle in the step (1) are as follows: the temperature is-15 to 15 ℃, the pressure is 1 to 10MPa, and preferably 4 to 10MPa. The pressure atmosphere can be one or more of air, nitrogen or inert gas. The reaction conditions for neutralizing and gelling in the step (1) are as follows: the pH value is 2 to 6, preferably 2 to 5, and the reaction time is 10 to 180 minutes, preferably 10 to 60 minutes (when continuous production is employed, the reaction time is the residence time of the acidic solution I and the alkaline solution I into the first reaction vessel). The neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 150 to 500rad/min.
In the method of the invention, the components of the acid solution I and the alkaline solution I introduced into the hydrogenation catalyst comprise aluminum oxide and hydrogenation active metals, namely first aluminum oxide and first hydrogenation active metals, and the components of the acid solution II or the alkaline solution II introduced into the hydrogenation catalyst comprise aluminum oxide and hydrogenation active metals, namely second aluminum oxide and second hydrogenation active metals. The hydrogenation active metal is at least one of the metals of the VIB group and the VIII group, the metal of the VIB group is preferably at least one of Mo and W, and the metal of the VIII group is preferably at least one of Ni and Co. The first hydrogenation active metal and the second hydrogenation active metal may be the same or different. The mass ratio of the first alumina to the second alumina is 1:5-5:1. The mass ratio of the first hydrogenation active metal to the second hydrogenation active metal in terms of oxide is 1:10-10:1. Preferably, the first hydrogenation active metal is selected from a first group VIB metal and a first group VIII metal, the second hydrogenation active metal is selected from a second group VIB metal and a second group VIII metal, further preferably, the mass ratio of the first group VIB metal to the second group VIB metal in terms of oxide is 1:8 to 8:1, and the mass ratio of the first group VIII metal to the second group VIII metal in terms of oxide is 1:8 to 8:1.
In the process of the present invention, the acidic solution I and the basic solution I in the neutralization gel in the step (1) may be selected according to a conventional coprecipitation method. The acidic solution I and the alkaline solution I may be aqueous solutions. The first alumina source is selected from at least one of an acidic aluminum source and a basic aluminum source, and can be introduced into the hydrogenation catalyst along with the acidic solution or the basic solution according to the acid-base property of the solution. The acidic aluminum source may be selected from AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of them, preferably Al 2 (SO 4 ) 3 、AlCl 3 One or more of them. The alkaline aluminum source may be selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 . The first hydrogenation active metal source may be introduced into the hydrogenation catalyst with an acidic or basic solution as determined by the acid base of its solution. The first hydrogenation active metal source is, for example, ammonium molybdate or molybdic acid, sodium tungstate, ammonium metatungstate or tungstic acid is used as the tungsten source, one or more of nickel nitrate, nickel chloride and basic nickel carbonate is used as the nickel source, and one or more of cobalt nitrate, cobalt chloride and basic cobalt carbonate is used as the cobalt source. The concentration of the acidic solution I is 10-100 g/100mL in terms of oxide, and the concentration of the alkaline solution I is 10-100 g/100mL in terms of oxide. For example, acidity The solution I is an acidic aluminum source solution, and the alkaline solution I is an alkaline active metal solution or a mixture of the alkaline active metal solution and the alkaline aluminum source solution; for example, if the acidic solution I is an acidic active metal solution, the alkaline solution I is an alkaline aluminum source solution or the alkaline active metal solution and the alkaline aluminum source solution are mixed; for example, if the acidic solution I is a mixed solution of an acidic aluminum source solution and an acidic active metal solution, the alkaline solution I is an alkaline active metal solution or a mixed solution of an alkaline active metal solution and an alkaline aluminum source solution or an alkaline aluminum source solution.
In the method of the invention, the organic solvent and the polar metal seed crystal are added into the first reaction kettle in parallel, wherein the adding rate of the organic solvent is the ratio of the adding rate of the acid solution I to the adding rate of the alkaline solution I in terms of volume of the two to be 0.1:1 to 10:1, preferably 0.1:1 to 5:1, the addition rate of the polar metal seed crystal is that the acid solution I and the alkaline solution I are added with Al 2 O 3 And the mass of the hydrogenation active metal oxide is 0.1 to 10%, preferably 0.2 to 5%.
In the method of the invention, the particle size distribution of the sol II obtained in the step (2) is as follows: the proportion of the crystal grains with the grain diameter smaller than 100nm is 0.5-5.0%, the proportion of the crystal grains with the grain diameter of 100-200 nm is 2-5%, and the proportion of the crystal grains with the grain diameter larger than 200nm is 90-95%.
In the method of the present invention, the operating conditions of the settling tank of step (2) are as follows: the temperature is-15 to 15 ℃, the pressure is 1 to 10MPa, and preferably 4 to 10MPa.
In the method, after the sedimentation in the step (2), the organic solvent on the upper layer can be recycled to the first reaction kettle for continuous use.
In the method of the invention, the operation conditions of the second reaction kettle in the step (3) are as follows: the temperature is 100 to 300 ℃, preferably 100 to 200 ℃, the pressure is 5 to 20MPa, preferably 10 to 20MPa, and more preferably 10 to 18MPa. Preferably, the operating pressure of the second reactor is at least 1MPa, more preferably at least 2MPa, higher than the operating pressure of the first reactor. The reaction conditions for neutralizing and gelling in the step (3) are as follows: the pH value is 7 to 12, preferably 7.5 to 10.0, and the reaction time is 10 to 180 minutes, preferably 10 to 120 minutes (when continuous production is employed, the reaction time is the residence time of the sol II with the acidic solution II or the alkaline solution II into the second reaction vessel). The neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 200 to 500rad/min.
In the process of the present invention, the acidic solution II and the basic solution II in the neutralization gel in the step (3) may be selected according to a conventional coprecipitation method. The acidic solution II and the alkaline solution II can be aqueous solutions. The second alumina source is at least one selected from an acidic aluminum source and a basic aluminum source, and can be introduced into the hydrogenation catalyst along with the acidic solution or the basic solution according to the acid-base property of the solution. The acidic aluminum source may be selected from AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of them, preferably Al 2 (SO 4 ) 3 、AlCl 3 One or more of them. The alkaline aluminum source may be selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 . The second hydrogenation active metal source may be introduced into the hydrogenation catalyst with the acidic or basic solution as determined by the acid base of its solution. The second hydrogenation active metal source is, for example, ammonium molybdate, molybdic acid or molybdenum oxide, the tungsten source is sodium tungstate, ammonium metatungstate or tungstic acid, the nickel source is one or more of nickel nitrate, nickel chloride and basic nickel carbonate, and the cobalt source is one or more of cobalt nitrate, cobalt chloride and basic cobalt carbonate. The concentration of the acid solution II is 10-100 g/100mL in terms of oxide, and the concentration of the alkaline solution II is 10-100 g/100mL in terms of oxide. For example, the acidic solution II is an acidic aluminum source solution, and the alkaline solution II is an alkaline active metal solution or a mixture of an alkaline active metal solution and an alkaline aluminum source solution; for another example, the acidic solution II is an acidic active metal solution, and the alkaline solution II is an alkaline aluminum source solution or a mixture of the alkaline active metal solution and the alkaline aluminum source solution; for another example, the acidic solution II is a mixed solution of an acidic aluminum source solution and an acidic active metal solution, and the alkaline solution II is an alkaline active metal solution or a mixed solution of an alkaline active metal solution and an alkaline aluminum source solution or an alkaline aluminum source solution.
In the method of the present invention, the aging reaction conditions of step (4): the temperature is 200-400 ℃, the pressure is 15-20.0 MPa, and the aging time is 100-360 min, preferably 150-250 min; the aging is carried out under stirring conditions, preferably at a stirring speed of 500 to 800r/min.
In the method of the invention, the drying temperature in the step (5) is 100-450 ℃, preferably 150-400 ℃ and the drying time is 1-10 hours, and the drying mode can be flash evaporation drying, cyclone drying, oven drying, spray drying and the like. The roasting temperature is 300-800 ℃, preferably 350-550 ℃, the roasting time is 2-5 hours, preferably 2-4 hours, and the roasting atmosphere is one or more of air, nitrogen, water vapor and the like.
The third aspect of the invention provides an application of the hydrogenation catalyst in the hydrogenation of inferior heavy oil.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the preparation method of the hydrogenation catalyst, firstly, an organic solvent which is not mutually soluble with water is used as a reaction medium, polar metal salt is used as a seed crystal, neutralization reaction is carried out under higher pressure and lower reaction temperature, on one hand, the generated sol-gel particles are wrapped by hydrophilic hydroxyl on the surface, all sol-gel particles in the organic solvent which is not mutually soluble with water are not adhered, under the action of the polar seed crystal, the characteristics of small molecule and large polarity and larger directional rate are utilized, so that crystal form precipitation or colloidal particles with crystal structures are easy to form, on the other hand, the Brownian movement of sol-gel molecules or ions is reduced under higher pressure and lower temperature, aggregation into clusters due to continuous collision of particles is reduced, the amorphous particles are dissolved under lower pH value, namely acid condition, the generated complete particles are kept, and then the crystal particles with complete crystal form are suitable and complete in the sol-gel particles under the conditions of high temperature, high pressure and high pH value, namely alkaline condition, the crystal form precipitation particles are easy to form, large particle size distribution and large particle size distribution are realized, and large particle size distribution of the obtained crystal form particles are easy to concentrate.
2. In the preparation method of the hydrogenation catalyst provided by the invention, the organic solvent can be complexed with the metal particles to form metal chelate in the coprecipitation process, and finally a large amount of chelated active metal is exposed in the roasting process, so that the metal utilization rate is provided, and the activity of the catalyst is greatly improved.
3. The catalyst provided by the invention has the characteristics of large surface area, large pore volume, concentrated particle size distribution and the like, and is particularly suitable for being used as a hydrogenation catalyst for hydrotreating heavy inferior raw materials, such as residual oil, wax oil, coal tar, coal liquefied oil and the like.
Drawings
FIG. 1 is a schematic flow chart of a continuous hydrogenation catalyst preparation;
wherein, the reference numerals are as follows: i-a first reaction kettle; II, III-settling tanks; IV-a second reaction kettle; v-aging the kettle; a-acidic solution I; b-alkaline solution I; c-polar metal seed; d-an organic solvent; e-setting tank II control valve; f-setting tank III control valve; g-sol II; h-acidic solution II or alkaline solution II; i-a second reaction kettle drain valve; j-overflow liquid; k-ageing cauldron drain valve.
Detailed Description
The method for preparing the hydrogenation catalyst of the present invention will be described in more detail by way of specific examples. The examples are merely illustrative of specific embodiments of the method of the invention and do not constitute a limitation on the scope of the invention.
The flow (shown in figure 1) for continuously preparing the hydrogenation catalyst provided by the invention comprises the following steps:
(1) Adding an organic solvent D, a polar metal seed crystal C, an acidic solution IA and an alkaline solution IB into a first reaction kettle I in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a sedimentation tank II or III for sedimentation, and is separated through a sedimentation tank II control valve E or a sedimentation tank III control valve F to obtain a lower layer, namely sol II G, and an upper layer, namely organic solvent;
(3) The sol II and an acidic solution II or an alkaline solution IIH flow in parallel and enter a second reaction kettle IV for neutralization and gel formation reaction to obtain a generated liquid III;
(4) The generated liquid III passes through a second reaction kettle liquid discharge valve I, and overflow liquid J enters an aging kettle V for aging;
(5) The ageing material obtained in the step (4) is discharged through the ageing kettle drain valve K, and then dried and roasted to obtain the hydrogenation catalyst;
the components of the acid solution I and the alkaline solution I introduced into the hydrogenation catalyst comprise first alumina and first hydrogenation active metals, and the components of the acid solution II or the alkaline solution II introduced into the hydrogenation catalyst comprise second alumina and second hydrogenation active metals.
In the present invention, "first", "second", etc. are used to distinguish between two different elements or portions, such as a first reaction vessel and a second reaction vessel, and are not intended to limit the specific location or relative relationship. Alternatively, "first", "second", etc. are introduced to distinguish between two different steps, such as a first alumina and a second alumina, and the first hydrogenation-active metal and the second hydrogenation-active metal are not intended to limit the specific composition thereof. In other words, in some embodiments, the terms "first," "second," etc. may also be interchanged with one another.
In the invention, the specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen adsorption method; the particle size distribution was measured using a laser particle size distribution meter.
In the examples and the comparative examples of the present invention, the Mo-Ni acidic active metal solution is a mixed solution of Mo-Ni-and is prepared from molybdenum oxide, basic nickel carbonate and phosphoric acid, wherein MoO 3 And the mass ratio of NiO is 4: concentration of 1, mo-Ni acidic active Metal solution in MoO 3 And a NiO meter; the Mo-Ni alkaline active metal solution is Mo-Ni-NH 3 Is prepared from ammonium molybdate, nickel nitrate and ammonia water, wherein MoO 3 And the mass ratio of NiO is 4: concentration of 1, mo-Ni alkali active metal solution in MoO 3 And a NiO meter.
Example 1
The flow of the hydrogenation catalyst prepared in this example is shown in FIG. 1.
2L of n-hexanol was added as a reaction medium to 10L of the first reaction vessel I, 1.6g of AgCl was added, the pressure of the first reaction vessel I was adjusted to 7MPa, the temperature was-15℃and the atmosphere was nitrogen, and the stirring rate was 200rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and the dripping concentration of Al is controlled at the flow rate of 20mL/min 2 O 3 A mixed solution of 50g/100mL of aluminum sulfate and 15g/100mL of Mo-Ni acidic active metal solution was added dropwise with Al at a flow rate of 15mL/min 2 O 3 The mixed solution of sodium metaaluminate with the concentration of 100g/100mL and Mo-Ni alkaline active metal with the concentration of 20g/100mL is reacted for 15min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II, simultaneously n-hexanol and AgCl are respectively added into a first reaction tank I at the rates of 10mL/min and 0.1g/min, after the generated liquid volume in the settling tank II reaches 1/2, the generated liquid is switched into a settling tank III, the organic solvent in the settling tank II and the sol II are separated, the organic solvent can be recycled into the first reaction tank I, and the property of the sol II A is shown in the table 1.
2.5L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 10MPa, the temperature is 180 ℃, and the stirring speed is 300rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 25g/min and Al at a flow rate of 15mL/min 2 O 3 And (3) mixing sodium metaaluminate with the concentration of 100g/100mL and Mo-Ni alkaline active metal with the concentration of 20g/100mL, adjusting the pH value of the reaction to 7.5, carrying out neutralization reaction for 60min, and discharging the generated liquid III out of the second reaction kettle.
The resulting solution III was fed into an aging vessel, the pressure of the aging vessel was adjusted to 15MPa, the temperature was 280℃and the stirring rate was 500rad/min, and after aging for 150min, it was dried by filtration at 150℃for 4 hours, and calcined at 400℃for 3 hours under an air atmosphere to give a catalyst A having the composition and properties shown in Table 2.
Example 2
The flow of the hydrogenation catalyst prepared in this example is shown in FIG. 1.
To 10L of the first reaction vessel I was added 2.5L of cyclohexane as a reaction9g of ZnS is added to the reaction medium, the pressure of the first reaction kettle I is regulated to 4MPa, the temperature is 0 ℃, the atmosphere is air, and the stirring speed is 300rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 45mL/min 2 O 3 A mixed solution of aluminum sulfate with a concentration of 100g/100mL and a Mo-Ni acidic active metal solution with a concentration of 30g/100mL was prepared, and Al was added dropwise at a flow rate of 30mL/min 2 O 3 The mixed solution of sodium metaaluminate with the concentration of 70g/100mL and Mo-Ni alkaline active metal with the concentration of 33g/100mL is reacted for 30min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II, cyclohexane and ZnS are respectively added into a first reaction kettle I at the rates of 15mL/min and 0.2g/min, after the generated liquid volume in the settling tank II reaches 3/4 of the generated liquid volume, the generated liquid is switched into a settling tank III, an organic solvent in the settling tank II is separated from a sol II, the organic solvent can be recycled into the first reaction kettle I, and the property of the sol II B is shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 10MPa, the temperature is 180 ℃, and the stirring speed is 300rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50g/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing solution of sodium metaaluminate with the concentration of 85g/100mL and Mo-Ni alkaline active metal with the concentration of 25g/100mL, wherein the pH value is 7.5, and after neutralization reaction for 120min, the generated liquid III is discharged out of the second reaction kettle.
The resulting solution III was fed into an aging vessel, the pressure of the aging vessel was adjusted to 20MPa, the temperature was 250 ℃, the stirring rate was 500rad/min, and after aging for 180min, the resulting solution was dried at 180℃for 5 hours by filtration, and calcined at 350℃for 4 hours under an air atmosphere to give a catalyst B, the composition and properties of which are shown in Table 2.
Example 3
The flow of the hydrogenation catalyst prepared in this example is shown in FIG. 1.
Adding 5L of benzoic acid as a reaction medium into a 10L first reaction kettle I, adding 13g of CuS, regulating the pressure of the first reaction kettle I to 8MPa, regulating the temperature to 15 ℃ and stirring the mixture at a speed, wherein the atmosphere is airThe rate was 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 50mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 80g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 35g/100mL was prepared, and Al was added dropwise at a flow rate of 40mL/min 2 O 3 The mixed solution of sodium metaaluminate with the concentration of 70g/100mL and Mo-Ni alkaline active metal with the concentration of 40g/100mL is reacted for 60min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II after neutralization reaction, meanwhile, benzoic acid and CuS are respectively added into a first reaction tank I at the rates of 20mL/min and 0.5g/min, after the generated liquid volume in the settling tank II reaches 2/3 of the generated liquid volume, the generated liquid is switched into a settling tank III, an organic solvent in the settling tank II is separated from a sol II, the organic solvent can be recycled into the first reaction tank I, and the property of the sol II C is shown in a table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 12MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50g/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing the sodium metaaluminate with the concentration of 60g/100mL and the Mo-Ni alkaline active metal with the concentration of 25g/100mL, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 15MPa, the temperature to 300 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3h at 200 ℃ by filtering, and roasting for 4h at 500 ℃ in an air atmosphere to obtain a catalyst C, wherein the composition and the properties are shown in Table 2.
Example 4
The flow of the hydrogenation catalyst prepared in this example is shown in FIG. 1.
4L of styrene is added into a 10L first reaction kettle I as a reaction medium, 7g of HgS is added, the pressure of the first reaction kettle I is regulated to 9MPa, the reaction temperature is 5 ℃, the atmosphere is air, and the stirring speed is 500rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid at the upper end of the first reaction kettle are opened A feed inlet for controlling the Al to be added dropwise at the flow rate of 100mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 50g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 25g/100mL was prepared, and Al was added dropwise at a flow rate of 150mL/min 2 O 3 The mixed solution of sodium metaaluminate with the concentration of 60g/100mL and Mo-Ni alkaline active metal with the concentration of 25g/100mL is reacted for 4.5, after neutralization reaction is carried out for 45min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a high-pressure sedimentation tank II, meanwhile, styrene and HgS are respectively added into the high-pressure sedimentation tank I at the rates of 30mL/min and 0.5g/min, after the generated liquid volume in the high-pressure sedimentation tank II reaches 4/5, the high-pressure sedimentation tank III is switched, and the organic solvent in the high-pressure sedimentation tank II and the sol II are separated, wherein the organic solvent can be recycled into the first reaction tank I, and the properties of the sol II D are shown in table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 15MPa, the temperature is 190 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 80g/min and Al at a flow rate of 100mL/min 2 O 3 And (3) mixing sodium metaaluminate with the concentration of 60g/100mL and Mo-Ni alkaline active metal with the concentration of 15g/100mL, adjusting the pH value of the reaction to 7.5, carrying out neutralization reaction for 80min, and discharging the generated liquid III out of the second reaction kettle.
The resulting solution III was fed into an aging vessel, the pressure of the aging vessel was adjusted to 20MPa, the temperature was 400 ℃, the stirring rate was 500rad/min, after aging for 210min, the resulting solution was dried at 180℃for 2 hours by filtration, and calcined at 400℃for 3 hours under an air atmosphere to give alumina D, the composition and properties of which are shown in Table 2.
Comparative example 1
The flow of the comparative example for preparing a hydrogenation catalyst is shown in FIG. 1.
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to be normal, the temperature is 75 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 50mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 80g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 35g/100mL was prepared, and Al was added dropwise at a flow rate of 40mL/min 2 O 3 The mixed solution of sodium metaaluminate with the concentration of 70g/100mL and Mo-Ni alkaline active metal with the concentration of 40g/100mL is reacted for 60min, a lower overflow port control valve is opened to enable the generated liquid I to flow into a settling tank II after neutralization reaction, meanwhile, benzoic acid and CuS are respectively added into a first reaction tank I at the rates of 20mL/min and 0.5g/min, after the generated liquid volume in the settling tank II reaches 2/3 of the generated liquid volume, the generated liquid is switched into a settling tank III, an organic solvent in the settling tank II is separated from a sol II, the organic solvent can be recycled into the first reaction tank I, and the properties of the sol IIE are shown in Table 1.
3L of purified water is added into the second reaction kettle IV, the pressure normal pressure of the second reaction kettle is regulated, the temperature is 75 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50g/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing the sodium metaaluminate with the concentration of 60g/100mL and the Mo-Ni alkaline active metal with the concentration of 25g/100mL, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 15MPa, the temperature to 300 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3h at 200 ℃ by filtering, and roasting for 4h at 500 ℃ in an air atmosphere to obtain a catalyst E, wherein the composition and the properties of the catalyst E are shown in Table 2.
Comparative example 2
The flow of the comparative example for preparing a hydrogenation catalyst is shown in FIG. 1.
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 50mL/min 2 O 3 A mixed solution of 80g/100mL of aluminum sulfate and 35g/100mL of Mo-Ni acidic active metal solution, and at the same time, 40g/100mL of the mixed solutionThe Al is dripped at the flow rate of mL/min 2 O 3 And (3) mixing solution of sodium metaaluminate with the concentration of 70g/100mL and Mo-Ni alkaline active metal with the concentration of 40g/100mL, wherein the reaction pH value is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated solution I to flow into a settling tank II, meanwhile, benzoic acid is added into a first reaction kettle I at the rate of 20mL/min, after the generated solution volume in the settling tank II reaches 2/3, the generated solution is switched to a settling tank III, and an organic solvent in the settling tank II is separated from a sol II, wherein the organic solvent can be recycled into the first reaction kettle I, and the property of the sol II F is shown in table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 12MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50g/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing the sodium metaaluminate with the concentration of 60g/100mL and the Mo-Ni alkaline active metal with the concentration of 25g/100mL, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 15MPa, the temperature to 300 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3h at 200 ℃ by filtering, and roasting for 4h at 500 ℃ in an air atmosphere to obtain a catalyst F, wherein the composition and the properties are shown in Table 2.
Comparative example 3
The flow of the comparative example for preparing a hydrogenation catalyst is shown in FIG. 1.
5L of purified water is added into 10L of a first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 50mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 80g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 35g/100mL was prepared, and Al was added dropwise at a flow rate of 40mL/min 2 O 3 Sodium metaaluminate with a concentration of 70g/100mL and Mo-Ni alkaline active gold with a concentration of 40g/100mLAnd (3) after the neutralization reaction is carried out for 60min, opening a lower overflow port control valve to enable the generated liquid I to flow into a settling tank II, simultaneously adding benzoic acid and CuS into a first reaction kettle I at the rates of 20mL/min and 0.5g/min respectively, switching to a settling tank III after the generated liquid volume in the settling tank II reaches 2/3 of the generated liquid volume, and separating purified water from sol II, wherein the properties of sol IIG are shown in table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 12MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50g/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing the sodium metaaluminate with the concentration of 60g/100mL and the Mo-Ni alkaline active metal with the concentration of 25g/100mL, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 15MPa, the temperature to 300 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3h at 200 ℃ by filtering, and roasting for 4h at 500 ℃ in an air atmosphere to obtain a catalyst G, wherein the composition and the properties are shown in Table 2.
Comparative example 4
The flow of the comparative example for preparing a hydrogenation catalyst is shown in FIG. 1.
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 50mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 80g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 35g/100mL was prepared, and Al was added dropwise at a flow rate of 40mL/min 2 O 3 The mixed solution of 70g/100mL sodium metaaluminate and 40g/100mL Mo-Ni alkaline active metal has a reaction pH value of 4.5, and after neutralization reaction for 60min, the lower overflow port control valve is opened to enable the generated liquid I to flow into the settling tank II, and the generated liquid I flows into the first settling tank II at the same timeBenzoic acid and CuS are respectively added into the reaction kettle I at the rates of 20mL/min and 0.5g/min, the reaction kettle I is switched to the sedimentation tank III after the volume of the generated liquid in the sedimentation tank II reaches 2/3 of the volume of the generated liquid, and the organic solvent in the sedimentation tank II is separated from the sol II, so that the organic solvent can be recycled into the first reaction kettle I to obtain the sol II.
3L of purified water is added into the second reaction kettle IV, the pressure and the normal pressure of the second reaction kettle are regulated, the temperature is 15 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50g/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing the sodium metaaluminate with the concentration of 60g/100mL and the Mo-Ni alkaline active metal with the concentration of 25g/100mL, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 15MPa, the temperature to 300 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3H at 200 ℃ by filtering, and roasting for 4H at 500 ℃ in an air atmosphere to obtain a catalyst H, wherein the composition and the properties are shown in Table 2.
TABLE 1 Properties of Sol II obtained in examples and comparative examples
Sol number II A B C D E F G
Particle size distribution, percent
＜100nm 4.2 3.7 4.9 4.2 15.6 25.3 10.3
100～200nm 3.7 5.0 3.7 4.5 23.9 32.9 32.9
＞200nm 92.1 91.3 91.2 91.3 60.5 41.8 56.8
TABLE 2 catalyst composition and Properties obtained in examples and comparative examples
Catalyst numbering A B C D E F G H
Catalyst composition, wt%
MoO 3 51.1 50.2 49.6 51.4 51.5 52.5 51.5 50.9
NiO 10.4 11.6 12.8 10.6 11.5 12.1 11.5 11.8
Specific surface area, m 2 /g 341 300 321 329 195 170 150 169
Pore volume, mL/g 1.4 1.3 1.5 1.4 0.75 0.81 0.69 0.80
Can be several pore diameters, nm 170 180 200 195 100 98 110 109
Particle size distribution, percent
＜200μm 3.9 4.3 5.0 4.9 20.1 26.2 13.9 12.9
200～350μm 2.9 5.0 3.2 4.7 26.9 39.2 35.9 12.9
＞350μm 93.2 90.7 91.8 90.4 53.0 34.6 50.2 74.2
Evaluation test
This example is a comparative run of the catalysts of examples 1, 2, 3, 4 and comparative examples 1, 2, 3, 4 on a 100mL fixed bed mini-hydrotreater, fed by the following feed. The properties of the raw oil are shown in Table 3; the evaluation conditions are shown in Table 4; the evaluation results of the catalyst are shown in Table 5.
TABLE 3 Properties of raw oil
Raw oil Inferior residuum
Density (20 ℃), g.cm -3 0.98
Carbon residue, wt% 12.99
S，wt％ 4.2
Ni+V，μg·g -1 118.9
Table 4 evaluation of process conditions
Reaction temperature, DEG C 380
Partial pressure of reaction hydrogen, MPa 15.0
Liquid hourly space velocity, h -1 0.5
Hydrogen to oil volume ratio 1000
Table 5 evaluation results of catalysts obtained in examples and comparative examples
Catalyst numbering A B C D E F G H
HDS，％ 98 97 99 96 85 82 92 91
HD(Ni+V)，％ 95 98 97 98 90 89 91 89
HDCCR，％ 78 72 73 70 50 59 62 60
As can be seen from tables 2 and 5, the catalyst provided by the invention has the advantages of large specific surface area, high pore volume, large pore diameter, concentrated grain distribution, higher hydrogenation activity and suitability for hydrotreating catalysts of heavy inferior raw materials.

Claims (19)

1. A hydrogenation catalyst comprising alumina and a hydrogenation-active metal component having the following properties: the pore volume is 1.3-1.5 mL/g; specific surface area of 200-350 m 2 The pore size of the polymer/g may be less than or equal to 100nm, preferably 160 to 210nm.
2. The catalyst of claim 1, wherein the catalyst has a particle size distribution as follows: the proportion of the crystal grains with the grain diameter smaller than 200 mu m is 0.5% -5.0%, the proportion of the crystal grains with the grain diameter of 200-350 mu m is 2.0% -5.0%, and the proportion of the crystal grains with the grain diameter larger than 350 mu m is 90.0% -95.0%.
3. The catalyst according to claim 1, wherein the hydrogenation active metal is selected from at least one of group VIB and group VIII metals, the group VIB metal is selected from at least one of Mo, W, and the group VIII metal is selected from at least one of Ni, co.
4. The catalyst according to claim 1, wherein the catalyst comprises, based on the mass of the catalyst, 10 to 80% by mass of the hydrogenation-active metal, 20 to 90% by mass of the alumina, preferably 5 to 70% by mass of the group VIB metal, and 5 to 50% by mass of the group VIII metal.
5. The process for preparing a hydrogenation catalyst according to any one of claims 1 to 4 comprising:
(1) Adding an organic solvent, a polar metal seed crystal, an acidic solution I and an alkaline solution I into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II;
(3) The sol II and the acid solution II or the alkaline solution II flow into a second reaction kettle in parallel to be neutralized and gel to obtain a generated liquid III;
(4) The generated liquid III enters an aging kettle for aging;
(5) Drying and roasting the ageing material obtained in the step (4) to obtain the catalyst;
wherein, the components of the acid solution I and the alkaline solution I introduced into the hydrogenation catalyst comprise alumina and hydrogenation active metals, namely first alumina and first hydrogenation active metals, and the components of the acid solution II or the alkaline solution II introduced into the hydrogenation catalyst comprise alumina and hydrogenation active metals, namely second alumina and second hydrogenation active metals.
6. The process according to claim 5, wherein the process is carried out in a continuous manner.
7. The preparation method according to claim 6, wherein a plurality of settling tanks used in the step (2) and aging tanks used in the step (4) are arranged for switching; the first reaction kettle in the step (1) adopts an overflow type operation mode for discharging the generated liquid I out of the first reaction kettle, and the second reaction kettle in the step (3) adopts an overflow type operation mode for discharging the generated liquid III out of the second reaction kettle.
8. The preparation method according to claim 6, wherein when the hydrogenation catalyst is continuously prepared, when the first reaction kettle is started, an organic solvent and a polar metal seed crystal are added as a base solution, and then an acidic solution I and an alkaline solution I are added in parallel to neutralize and gel until a generated solution I starts to discharge from the first reaction kettle; wherein the addition amount of the organic solvent in the base solution is 1/5-1/3 of the actual effective use volume of the first reaction kettle, when the generated solution I is discharged out of the first reaction kettle, the acidic solution I and the alkaline solution I in the first reaction kettle are prepared by using Al 2 O 3 And the addition amount of the polar metal salt seed crystal is 0.1-5.0%, preferably 0.2-2.0% based on the total mass of the hydrogenation active metal oxide.
9. The preparation method according to claim 6, wherein when the continuous hydrogenation catalyst preparation is adopted, when the second reaction kettle is started, the bottom water is added first, then the sol II and the acid solution II or the alkaline solution II are added in parallel to neutralize and gel until the generated liquid III starts to be discharged from the second reaction kettle; wherein, the addition amount of the bottom water is 1/7-1/2, preferably 1/6-1/3 of the actual effective use volume of the second reaction kettle.
10. The process according to any one of claims 5 to 9, wherein the organic solvent in step (1) is an organic substance which is not miscible or slightly soluble with water and is selected from one or more of alkanes, alkenes, organic alcohols, organic acids; preferably, the organic matter has a carbon number of 5 to 12.
11. The method according to any one of claims 5 to 9, wherein the polar metal seed is selected from one or more of AgCl, znS, cuS and HgS.
12. The process according to any one of claims 5 to 9, wherein the first reaction vessel of step (1) is operated under the following conditions: the temperature is-15 to 15 ℃, the pressure is 1 to 10MPa, and the preferable pressure is 4 to 10MPa; the reaction conditions for neutralizing and gelling in the step (1) are as follows: the pH value is 2-6, preferably 2-5, and the reaction time is 10-180 minutes, preferably 10-60 minutes; the neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 150 to 500rad/min.
13. The production method according to any one of claims 5 to 9, wherein the mass ratio of the first alumina to the second alumina is 1:5 to 5:1, and the mass ratio of the first hydrogenation active metal to the second hydrogenation active metal in terms of oxide is 1:10 to 10:1.
14. The process according to any one of claims 5 to 9, wherein the organic solvent and the polar metal seed crystal are added to the first reaction vessel in parallel flow, wherein the addition rate of the organic solvent is such that the ratio of the addition rates of the acidic solution i and the basic solution i in terms of the sum of the two addition rates by volume is 0.1:1 to 10:1, preferably 0.1:1 to 5:1, the addition rate of the polar metal seed crystal is that the acid solution I and the alkaline solution I are added with Al 2 O 3 And the mass of the hydrogenation active metal oxide is 0.1 to 10%, preferably 0.2 to 5%.
15. The process according to any one of claims 5 to 9, wherein the particle size distribution of the sol ii obtained in step (2) is as follows: the proportion of the crystal grains with the grain diameter smaller than 100nm is 0.5-5.0%, the proportion of the crystal grains with the grain diameter of 100-200 nm is 2-5%, and the proportion of the crystal grains with the grain diameter larger than 200nm is 90-95%.
16. The process according to any one of claims 5 to 9, wherein the operating conditions of the settling tank of step (2) are as follows: the temperature is-15 to 15 ℃, the pressure is 1 to 10MPa, and preferably 4 to 10MPa.
17. The process according to any one of claims 5 to 9, wherein the second reactor of step (3) is operated under the following conditions: the temperature is 100-300 ℃, preferably 100-200 ℃, and the pressure is 5-20 MPa, preferably 10-20 MPa; the reaction conditions for neutralizing and gelling in the step (3) are as follows: the pH value is 7-12, preferably 7.5-10.0, and the reaction time is 10-180 minutes, preferably 10-120 minutes; the neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 200 to 500rad/min.
18. The method according to any one of claims 5 to 9, wherein in step (4), the aging reaction conditions are: the temperature is 200-400 ℃, the pressure is 15-20.0 MPa, and the aging time is 100-360 min, preferably 150-200 min; the aging is carried out under stirring conditions, preferably at a stirring speed of 500 to 800r/min.
19. The process according to any one of claims 5 to 9, characterized in that in step (5), the drying temperature is 100 to 450 ℃, preferably 150 to 400 ℃, and the drying time is 1 to 10 hours; the roasting temperature is 300-800 ℃, preferably 350-550 ℃, the roasting time is 2-5 hours, preferably 2-4 hours, and the roasting atmosphere is one or more of air, nitrogen or water vapor.
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WO2015029617A1 (en) * 2013-08-30 2015-03-05 Ｊｘ日鉱日石エネルギー株式会社 Hydrocarbon oil production method
WO2018019203A1 (en) * 2016-07-29 2018-02-01 武汉凯迪工程技术研究总院有限公司 Boron-modified hydrofining catalyst having high loading amount and preparation method therefor
CN108393091A (en) * 2017-02-08 2018-08-14 中国石油化工股份有限公司 Liquefied coal coil hydrotreating catalyst and the preparation method and application thereof
CN112516993A (en) * 2019-09-17 2021-03-19 中国石油化工股份有限公司 Preparation method of alumina carrier
CN112717964A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 Paraffin hydrofining catalyst and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110174691A1 (en) * 2010-01-21 2011-07-21 Michael Anthony Reynolds Process for treating a hydrocarbon-containing feed
WO2015029617A1 (en) * 2013-08-30 2015-03-05 Ｊｘ日鉱日石エネルギー株式会社 Hydrocarbon oil production method
WO2018019203A1 (en) * 2016-07-29 2018-02-01 武汉凯迪工程技术研究总院有限公司 Boron-modified hydrofining catalyst having high loading amount and preparation method therefor
CN108393091A (en) * 2017-02-08 2018-08-14 中国石油化工股份有限公司 Liquefied coal coil hydrotreating catalyst and the preparation method and application thereof
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