[go: up one dir, main page]

CN114436303B - Macroporous alumina and preparation method and application thereof - Google Patents

Macroporous alumina and preparation method and application thereof Download PDF

Info

Publication number
CN114436303B
CN114436303B CN202011115929.0A CN202011115929A CN114436303B CN 114436303 B CN114436303 B CN 114436303B CN 202011115929 A CN202011115929 A CN 202011115929A CN 114436303 B CN114436303 B CN 114436303B
Authority
CN
China
Prior art keywords
alumina
solution
slurry
pore volume
filter cake
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011115929.0A
Other languages
Chinese (zh)
Other versions
CN114436303A (en
Inventor
王继锋
刘奕
姜虹
杨占林
王会刚
丁思佳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN202011115929.0A priority Critical patent/CN114436303B/en
Publication of CN114436303A publication Critical patent/CN114436303A/en
Application granted granted Critical
Publication of CN114436303B publication Critical patent/CN114436303B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
    • C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/66—Pore distribution
    • B01J35/695—Pore distribution polymodal
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention discloses a macroporous alumina, a preparation method and application thereof, wherein the method comprises the following steps: mixing the material obtained after the neutralization reaction of the aluminum source with lignin to form slurry, and standing at 50-90 ℃ for 30-180min; adding acid liquor to adjust the pH of the slurry to be less than 7, stirring and filtering to obtain an aged filter cake, and drying to obtain pseudo-boehmite; and roasting the pseudo-boehmite to obtain the alumina. The alumina carrier prepared by the method has large pore volume, high specific surface area and proper pore distribution.

Description

Macroporous alumina and preparation method and application thereof
Technical Field
The invention relates to a catalytic carrier material, in particular to macroporous alumina, a preparation method and application thereof.
Background
γ-Al 2 O 3 Is a carrier material commonly used in the petrochemical industry field, and the structural morphology of the precursor boehmite basically determines the final generation of gamma-Al 2 O 3 The morphology of pseudo-boehmite, therefore, the microstructure, grain shape, size and manner of stacking all can affect the properties of the final catalyst produced. With the continuous improvement of the oil quality requirement, the catalyst is required to have proper pore structure property, so that the carrier is also required to have larger pore volume and pore diameter and relatively concentrated pore distribution, thereby being beneficial to the diffusion and mass transfer of macromolecules; in addition, the carrier is also required to have a large specific surface area so that the active ingredient can be sufficiently dispersed.
When preparing the macroporous carrier, the most common and simplest reaming method is to add the reaming agent in the process of extruding strips, but the method can reduce the mechanical strength of the carrier; the addition of a pore-expanding agent in the gelling process is also one of the pore-expanding methods, and NaAlO is adopted 2 -Al 2 (SO 4 ) 3 For the preparation of active alumina as raw material, the production process mainly comprises the steps of neutralization and gel formation, aging, water washing, forming, drying, activation roasting and the like, but the performance of the prepared alumina has larger difference due to different process conditions and hole enlarging measures.
CN102039195a discloses a method for preparing alumina. The method is to add an organic pore-expanding agent and a defoaming agent in the gelling process and control the size and distribution of bubbles, so that the alumina has large pore volume and large pore diameter, and the pore distribution is concentrated and the macropores are uniformly distributed.
CN102730724a discloses a preparation method of alumina carrier, the process is that aluminium sulfate solution and sodium metaaluminate solution are glued in stainless steel neutralization kettle by continuous parallel flow method, then after aging in stainless steel aging water washing tank for a certain time, the stainless steel aging water washing tank is pressed into plate-frame filter press by pressing pump to make continuous washing, so as to obtain pseudo-boehmite primary particles with large crystal grains, the unloaded filter cake is acidified, proper amount of pore-expanding agent and surfactant are added in the acidification process to make formation, the formed wet ball is dried in drying box, and the dried ball is calcined and reamed in roasting activation furnace at high temperature. The process has the characteristics of low cost, small equipment corrosion, continuous cyclic washing, low waste liquid discharge, small pollution and the like.
CN108975366a provides a method for preparing macroporous pseudo-boehmite. Comprising the following steps: blending the alumina concentration in the sodium aluminate solution meeting the index requirement to a preset concentration, and then cooling to a preset temperature to obtain a first solution; adding a pore-expanding agent into the first solution, and forming a gel under a preset condition to obtain a first colloid; and (3) washing and drying the aged first colloid.
CN103771469a discloses a method for preparing an alumina carrier. The method comprises the following steps: adding gemini surfactant into acid aluminum salt solution and alkaline aluminate solution before or during the parallel flow gel forming process to ream, aging after gel forming, filtering, washing, drying, molding, drying and roasting to obtain the alumina carrier.
CN101462074a discloses an alumina carrier and a method for preparing the same. The carrier is prepared by adopting a small amount of starch and/or carbon black as seed crystals, preparing slurry containing aluminum hydroxide by adopting a parallel flow and back swing method, and then regulating the pH value by using ammonium carbonate and/or ammonium bicarbonate to finally obtain the alumina carrier. The alumina obtained by the method still maintains higher strength under the condition of expanding pore volume and pore diameter.
CN101618886a discloses an aluminium hydroxide and a process for its preparation. The method specifically comprises the following steps: adding a small amount of organic pore-expanding agent and defoamer into the sodium metaaluminate aqueous solution, and then introducing air and CO 2 The mixed gas is utilized to stir and form gel at one time to generate pseudo-boehmite with uniform grains, and the pseudo-boehmite is roasted to obtain the alumina with large pore volume, large pore diameter and concentrated pore distribution.
The above method has the following disadvantages: when the pore-expanding agent is a water-insoluble solid, the uniform dispersion of the pore-expanding agent cannot be ensured by simple physical mixing; when the pore expanding agent is soluble salt, the pore expanding agent acts as a soft template agent, and shrinkage of the pore canal is difficult to avoid during roasting.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a macroporous alumina carrier, a preparation method and application thereof.
The invention relates to a preparation method of macroporous alumina, which comprises the following steps:
mixing the material obtained after the neutralization reaction of the aluminum source with lignin to form slurry, and placing for 30-180min at 50-90 ℃, preferably aging the material obtained after the neutralization reaction of the aluminum source, washing and filtering to obtain a wet filter cake, mixing the wet filter cake with lignin to form slurry, and controlling the pH of the slurry to be more than 7, preferably 7.5-9;
adding acid liquor to adjust the pH of the slurry to be less than 7, stirring and filtering to obtain an aged filter cake, and drying to obtain pseudo-boehmite;
and roasting the pseudo-boehmite to obtain the alumina.
A non-limiting preparation method of macroporous alumina, comprising the steps of:
(1) Preparing sodium metaaluminate solution and aluminum sulfate solution with certain concentration;
(2) The two solutions obtained in the step (1) are subjected to gel forming reaction in a gel forming kettle by a parallel flow method, and a neutralization material is obtained;
(3) Aging, washing and filtering the product obtained in the step (2) to obtain a wet filter cake;
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH of the slurry to be more than 7, adding lignin into the slurry, standing for 30-180min at 50-90 ℃ to obtain a material, adding acid liquor into the material to adjust the pH of the slurry to be less than 7, stirring and filtering to obtain an aged filter cake, and drying to obtain pseudo-boehmite;
(5) And roasting the pseudo-boehmite to obtain the alumina.
In the above method, the concentration of the sodium metaaluminate solution in the step (1) is 100-250gAl 2 O 3 The concentration of the aluminum sulfate solution is 20-90gAl 2 O 3 /L。
In the method, the glue forming temperature in the step (2) is controlled to be 30-90 ℃, preferably 40-70 ℃, and the glue forming is stopped when the pH value reaches 6-10.
In the method, the aging temperature in the step (3) is 60-140 ℃ and the aging time is 1-3 h.
In the above method, step (3) uses distilled water at a temperature of 60 to 80 ℃ to perform the washing.
In the above method, the lignin in the step (4) is at least one of alkali lignin, enzymatic lignin and lignin sulfonate.
In the method, the lignin in the step (4) accounts for 1-5% of the mass of the sodium metaaluminate in the solution.
In the above method, the acid in step (4) is an organic acid such as acetic acid, citric acid, tartaric acid, etc., preferably citric acid, and the pH is adjusted to less than 7, preferably 4-6.5.
In the above method, the drying temperature in step (4) is 70 ℃ to 140 ℃, preferably 80 ℃ to 120 ℃, and the drying time is 2h to 20h, preferably 6h to 12h.
In the above method, the roasting temperature in the step (5) is 400-850 ℃, preferably 450-650 ℃, and the roasting time is 2-6 h, preferably 3-5 h.
The properties of the alumina described in the above method are as follows: pore volume is 0.70-1.50mL/g, preferably 0.85-1.30mL/g; specific surface area of 200-420m 2 /g, preferably 260-330m 2 /g; the most probable pore size is 12-20nm, preferably 14-18nm, and the pore distribution is as follows: the pore volume of the pores with the pore diameter smaller than 10nm accounts for less than 10 percent, preferably less than 8 percent, the pore volume of the pores with the pore diameter of 10-20 nm accounts for 60-80 percent, preferably 70-80 percent, and the pore volume of the pores with the pore diameter larger than 20nm accounts for 10-20 percent, preferably 14-18 percent of the total pore volume.
The hydrotreating catalyst containing the alumina contains active metals of the VIB group and/or the VIII group, wherein the active metals of the VIB group are W and/or Mo, the active metals of the VIII group are Co and/or Ni, the content of the oxides of the VIB group metals is 10-35%, preferably 10-30%, and the content of the oxides of the VIII group metals is 1-12%, preferably 2-8%. The tungsten is mainly one or two of ammonium metatungstate and ammonium tetrathiotungstate, the molybdenum is mainly one or more of molybdenum oxide, ammonium molybdate, ammonium tetrathiomolybdate and ammonium paramolybdate, the nickel is mainly one or more of nickel nitrate, nickel sulfamate, basic nickel carbonate, nickel oxalate, nickel chloride and nickel acetate, and the cobalt is mainly one or more of cobalt nitrate, cobalt oxalate, basic cobalt carbonate and cobalt chlorate. The concentration of the active component solution is 10wt% to 60wt%.
The application of the hydrotreating catalyst takes catalytic diesel oil as a raw material, and the reaction conditions are as follows: the total pressure of the reaction is 2-8MPa, and the liquid volume space velocity is 0.2h -1 ~4.0h -1 The volume ratio of hydrogen to oil is 200:1-2000:1, and the reaction temperature is 230-430 ℃.
Compared with the prior art, the technical scheme of the invention has the following advantages: based on the characteristic that lignin is sensitive to pH value, lignin is firstly dissolved in alkaline slurry, so that uniform dispersion of lignin in the slurry is ensured, after the pH value of the solution is reduced, lignin is separated out and converted into a hard template agent and is still uniformly distributed in alumina colloid, a good framework supporting effect is achieved in the roasting process, the shrinkage degree of pore channels is reduced, collapse of macropores is prevented, the pore size is improved, and mass transfer diffusion of macromolecular reactants is facilitated.
Detailed Description
The technical scheme of the invention is further described by the following examples, but the invention is not limited to the examples, and the percentages in the text of the invention are mass percent unless otherwise specified.
Example 1
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 60 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is 7.5, the pH value of the solution is about 3 hours, after neutralization, the reaction liquid is completely put into an aging tank, the aging temperature is controlled to be 60-80 ℃, the reaction liquid is aged for 60min and washed twice, and then the wet filter cake is obtained after filtration.
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH value of the slurry to be 8, adding 6g of alkali lignin into the slurry, continuing the aging reaction at 60 ℃ for 60min to obtain an aged material, adding citric acid to adjust the pH value of the slurry to be=6.5, continuing stirring for 10nim, filtering the material, and drying the aged filter cake at 120 ℃ to obtain the alumina dry gel powder Z1.
Example 2
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 60 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is 7.5, the pH value of the solution is about 3 hours, after neutralization, the reaction liquid is completely put into an aging tank, the aging temperature is controlled to be 60-80 ℃, the reaction liquid is aged for 60min and washed twice, and then the wet filter cake is obtained after filtration.
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH value of the slurry to be 8.5, adding 10g of alkali lignin into the slurry, continuing the aging reaction at 60 ℃ for 60min to obtain an aged material, adding acetic acid to adjust the pH value of the slurry to be=6, continuing stirring for 10nim, filtering the material, and drying the aged filter cake at 120 ℃ to obtain the alumina dry gel powder Z2.
Example 3
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 40 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is 6, the pH value of the solution is about 3 hours, after neutralization, the reaction liquid is completely put into an aging tank, the aging temperature is controlled to be 60-80 ℃, the reaction liquid is aged for 60 minutes and washed twice, and then the wet filter cake is obtained after filtration.
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH value of the slurry to be 8.5, adding 3g of enzymolysis lignin into the slurry, continuing the aging reaction at 60 ℃ for 60min to obtain an aged material, adding tartaric acid to adjust the pH value of the slurry to be=6, continuing stirring for 10nim, filtering the material, and drying the aged filter cake at 120 ℃ to obtain the alumina dry gel powder Z3.
Example 4
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 40 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is 6, the pH value of the solution is about 3 hours, after neutralization, the reaction liquid is completely put into an aging tank, the aging temperature is controlled to be 60-80 ℃, the reaction liquid is aged for 60 minutes and washed twice, and then the wet filter cake is obtained after filtration.
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH value of the slurry to be 8, adding 4g of enzymolysis lignin into the slurry, continuing aging reaction at 60 ℃ for 60min to obtain an aged material, adding acetic acid to adjust the pH=5 of the slurry, continuing stirring for 10nim, filtering the material, and drying the aged filter cake at 120 ℃ to obtain the alumina dry rubber powder Z4.
Example 5
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 60 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is adjusted to pH value of 8, about 3 hours, and the middle periodAnd after the completion of the reaction, putting the whole reaction liquid into an aging tank, controlling the aging temperature to be 60-80 ℃, aging for 60min, washing twice, and filtering to obtain a wet filter cake.
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH value of the slurry to be 9, adding 8g of alkali lignin into the slurry, continuing the aging reaction at 60 ℃ for 60min to obtain an aged material, adding citric acid to adjust the pH=5 of the slurry, continuing stirring for 10nim, filtering the material, and drying the aged filter cake at 120 ℃ to obtain the alumina dry gel powder Z5.
Example 6
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 60 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is 8, the pH value of the solution is about 3 hours, after neutralization, the reaction liquid is completely put into an aging tank, the aging temperature is controlled to be 60-80 ℃, the reaction liquid is aged for 60 minutes and washed twice, and then the wet filter cake is obtained after filtration.
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH value of the slurry to be 8, adding 10g of alkali lignin into the slurry, continuing aging reaction at 60 ℃ for 60min to obtain an aged material, adding citric acid to adjust the pH=5 of the slurry, continuing stirring for 10nim, filtering the material, and drying the aged filter cake at 120 ℃ to obtain the alumina dry rubber powder Z6.
Example 7
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 90 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is 9, the pH value of the solution is about 3 hours, after neutralization, the reaction liquid is completely put into an aging tank, the aging temperature is controlled to be 60-80 ℃, the reaction liquid is aged for 60 minutes and washed twice, and then the wet filter cake is obtained after filtration.
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH value of the slurry to be 7.5, adding 12.5g of sodium lignin sulfonate into the slurry, continuing the aging reaction at 60 ℃ for 60min to obtain an aged material, adding acetic acid to adjust the pH value of the slurry to be=4.5, continuing stirring for 10nim, filtering the material, and drying the aged filter cake at 120 ℃ to obtain the alumina dry adhesive powder Z7.
Example 8
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 90 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is 9, the pH value of the solution is about 3 hours, after neutralization, the reaction liquid is completely put into an aging tank, the aging temperature is controlled to be 60-80 ℃, the reaction liquid is aged for 60 minutes and washed twice, and then the wet filter cake is obtained after filtration.
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH value of the slurry to be 8, adding 6g of sodium lignin sulfonate into the slurry, continuing to perform aging reaction at 60 ℃ for 60min to obtain an aged material, adding tartaric acid to adjust the pH=5 of the slurry, continuing to stir for 10nim, filtering the material, and drying the aged filter cake at 120 ℃ to obtain the alumina dry gel powder Z8.
Comparative example 1
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 60 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is 7.5, the pH value of the solution is about 3 hours, after neutralization, the reaction liquid is completely put into an aging tank, the aging temperature is controlled to be 60-80 ℃, the reaction liquid is aged for 60min and washed twice, and then the wet filter cake is obtained after filtration.
(4) And (3) adding water into the wet filter cake, pulping to obtain slurry, and continuing an aging reaction at 60 ℃ for 60min to obtain an aging material, and drying the aging filter cake at 120 ℃ to obtain the alumina dry gel powder Z9.
Comparative example 2
（1）NaAlO 2 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, followed by 313.5g of NaAlO 2 After all dissolution, the solution was cooled to room temperature and water was added to prepare 1500ml of a 130g/L solution in terms of alumina.
（2）Al 2 (SO 4 ) 3 Preparing a solution: 1000ml of deionized water was heated to 60-70℃with mechanical stirring, and 294g of Al was then added 2 (SO 4 ) 3 ·18H 2 O, after all the solution was dissolved, the temperature was lowered to room temperature, and water was added to prepare 1500ml of a 30g/L solution in terms of alumina.
(3) Adding a proper amount of deionized water into a stainless steel reaction kettle, heating to 60 ℃ under mechanical stirring, and then performing parallel flow gelling. Stabilization of NaAlO 2 The flow rate of the solution is 3-25ml/min, and Al is regulated 2 (SO 4 ) 3 The flow rate of the solution is 7.5, the pH value of the solution is about 3 hours, after neutralization, the reaction liquid is completely put into an aging tank, the aging temperature is controlled to be 60-80 ℃, the reaction liquid is aged for 60min and washed twice, and then the wet filter cake is obtained after filtration.
(4) Adding water into the wet filter cake, pulping to obtain slurry, adding 6g of alkali lignin into the slurry, and continuing aging reaction at 60 ℃ for 60min to obtain an aged material, and drying the aged filter cake at 120 ℃ to obtain the alumina dry rubber powder Z10.
Example 9
Taking Z1-Z10 dry rubber powder, roasting at 600 ℃ for 3 hours to obtain alumina powder, wherein the pore structure of the alumina powder is shown in table 1.
Table 1 properties of alumina powder in examples and comparative examples
As can be seen from Table 1, the alumina powder obtained in the examples has a significantly increased pore volume and a more concentrated pore distribution, and is offset in the macroporous direction, as compared with the comparative examples, and is suitable for use as a catalyst support material.
Example 10
Taking 100g of the dry rubber powder of the examples and the comparative examples, adding 2g of sesbania powder and 2g of citric acid, dissolving 4.1g of nitric acid (68 wt%) in 150ml of deionized water to prepare an acidic solution, adding the acidic solution into the powder, rolling for 20min by a rolling machine, supplementing water according to the dryness and the humidity of a filter cake, extruding into 1.7mm clover strips on a strip extruder, drying for 6 hours at 120 ℃, and roasting for 3 hours at 600 ℃ to obtain the catalyst carrier.
The hydrogenation active component is loaded on the alumina carrier prepared by the method by adopting an impregnation method, the hydrogenation active component impregnation liquid is prepared by adopting a conventional method according to the composition of a target catalyst, the impregnation time is more than 6 hours by adopting an equal volume impregnation mode, and the impregnated carrier is dried and roasted to obtain the hydrotreating catalyst C1-C10. The drying condition is that the drying is carried out for 3-4 hours at 100-120 ℃, and the roasting condition is that the roasting is carried out for 3-6 hours at 400-600 ℃. The main physical properties of the catalyst are shown in Table 2.
TABLE 2 Primary physical Properties of the catalyst
The catalyst sulfiding used kerosene with a content of 5wt% dimethyl disulfide as sulfiding oil. The pre-vulcanization conditions were as follows: hydrogen partial pressure 4MPa, vulcanization temperature 370 ℃ and volume space velocity 1.0 h -1 Hydrogen oil volume ratio 1000. The reaction process conditions of the example catalyst and the comparative example catalyst are: the pressure is 14.7MPa, the airspeed is 1.0, the temperature is 340 ℃, and the hydrogen-oil volume ratio is 1000:1.
The catalysts of the above examples and comparative examples were subjected to activity evaluation tests in a micro-reactor using catalytic diesel as a raw material, and the properties are shown in Table 3. The catalyst is presulfided before use, the vulcanized oil is straight-run kerosene, 5wt% of DMDS (dimethyl disulfide) is added, and the presulfided raw oil is directly introduced into the raw oil for test reaction. The pre-vulcanization and test conditions are shown in Table 4, and the evaluation results are shown in Table 5
TABLE 3 Properties of the feedstock
TABLE 4 Presulfidation and test conditions
Table 5 evaluation results
As can be seen from the data in the table, the activity of the catalyst prepared by the method of the present invention is significantly higher than that of the catalyst prepared by the method of the comparative example.

Claims (19)

1. A preparation method of macroporous alumina is characterized in that: the method comprises the following steps:
aging the material obtained after the neutralization reaction of the aluminum source, washing and filtering to obtain a wet filter cake, mixing the wet filter cake with lignin to form slurry, controlling the pH of the slurry to be more than 7, and standing at 50-90 ℃ for 30-180min;
adding acid liquor to adjust the pH of the slurry to be less than 7, stirring and filtering to obtain an aged filter cake, and drying to obtain pseudo-boehmite;
and roasting the pseudo-boehmite to obtain the alumina.
2. The method according to claim 1, characterized in that: the method comprises the following steps:
(1) Preparing sodium metaaluminate solution and aluminum sulfate solution with certain concentration;
(2) The two solutions obtained in the step (1) are subjected to gel forming reaction in a gel forming kettle by a parallel flow method, and a neutralization material is obtained;
(3) Aging, washing and filtering the product obtained in the step (2) to obtain a wet filter cake;
(4) Adding water into the wet filter cake, pulping to obtain slurry, controlling the pH of the slurry to be more than 7, adding lignin into the slurry, standing for 30-180min at 50-90 ℃ to obtain a material, adding acid liquor into the material to adjust the pH of the slurry to be less than 7, stirring and filtering to obtain an aged filter cake, and drying to obtain pseudo-boehmite;
(5) And roasting the pseudo-boehmite to obtain the alumina.
3. The method according to claim 2, characterized in that: the concentration of the sodium metaaluminate solution in the step (1) is 100-250gAl 2 O 3 The concentration of the aluminum sulfate solution is 20-90gAl 2 O 3 /L。
4. The method according to claim 2, characterized in that: and (2) controlling the glue forming temperature to be 30-90 ℃.
5. The method according to claim 2, characterized in that: the aging temperature in the step (3) is 60-140 ℃ and the aging time is 1-3 h.
6. The method according to claim 2, characterized in that: and (3) washing by distilled water with the temperature of 60-80 ℃.
7. The method according to claim 2, characterized in that: the lignin in the step (4) is at least one of alkali lignin, enzymatic hydrolysis lignin and lignin sulfonate.
8. The method according to claim 2, characterized in that: the lignin dosage in the step (4) accounts for 1-5% of the mass of sodium metaaluminate in the solution.
9. The method according to claim 2, characterized in that: in the step (4), the acid is at least one of acetic acid, citric acid and tartaric acid, and the pH value is regulated to be less than 7.
10. The method according to claim 2, characterized in that: in the step (4), the acid is at least one of acetic acid, citric acid and tartaric acid, and the pH is adjusted to 4-6.5.
11. The method according to claim 2, characterized in that: the temperature of the drying in the step (4) is 70-140 ℃ and the time is 2-20 h.
12. The method according to claim 11, wherein: the temperature of the drying in the step (4) is 80-120 ℃ and the time is 6-12 h.
13. The method according to claim 2, characterized in that: the roasting temperature in the step (5) is 400-850 ℃ and the roasting time is 2-6 h.
14. The method according to claim 13, wherein: the roasting temperature in the step (5) is 450-650 ℃ and the roasting time is 3-5 h.
15. Alumina prepared by the process according to any one of claims 1 to 14, characterized in that: the properties of the alumina are as follows: pore volume is 0.70-1.50mL/g; specific surface area of 200-420m 2 /g; the most probable pore diameter is 12-20nm; the pore distribution is as follows: the pore volume of the pores with the pore diameter less than 10nm accounts for less than 10 percent of the total pore volume; the pore volume of the pores with the pore diameter of 10-20 nm accounts for 60-80% of the total pore volume; the pore volume of the pores with the pore diameter more than 20nm accounts for 10 to 20 percent of the total pore volume.
16. The alumina of claim 15, wherein: the properties of the alumina are as follows: pore volume is 0.85-1.30mL/g; specific surface area of 260-330m 2 /g; the most probable pore size is 14-18nm, and the pore distribution is as follows: the pore volume of the pores with the pore diameter smaller than 10nm accounts for less than 8 percent of the total pore volume, the pore volume of the pores with the pore diameter of 10-20 nm accounts for 70-80 percent of the total pore volume, and the pore volume of the pores with the pore diameter larger than 20nm accounts for 14-18 percent of the total pore volume.
17. A hydrotreating catalyst characterized by: the catalyst takes the alumina as a carrier according to claim 15 or 16, the hydrotreating catalyst contains active metals of the VIB group and/or the VIII group, the active metals of the VIB group are W and/or Mo, the active metals of the VIII group are Co and/or Ni, the mass content of the oxides of the VIB group is 10-35% and the mass content of the oxides of the VIII group is 1-12% based on the weight of the final hydrotreating catalyst.
18. The hydrotreating catalyst according to claim 17, wherein: the mass content of the VIB group metal oxide is 10-30% and the mass content of the VIII group metal oxide is 2-8% based on the weight of the final hydrotreating catalyst.
19. Use of the catalyst according to claim 17, characterized in that: catalytic diesel oil is used as raw material, and the reaction condition is that
The following are provided: the total pressure of the reaction is 2-8MPa, and the liquid volume space velocity is 0.2h -1 ～4.0h -1 The volume ratio of the hydrogen to the oil is 200:1-2000:1,
the reaction temperature is 230-430 ℃.
CN202011115929.0A 2020-10-19 2020-10-19 Macroporous alumina and preparation method and application thereof Active CN114436303B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011115929.0A CN114436303B (en) 2020-10-19 2020-10-19 Macroporous alumina and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011115929.0A CN114436303B (en) 2020-10-19 2020-10-19 Macroporous alumina and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114436303A CN114436303A (en) 2022-05-06
CN114436303B true CN114436303B (en) 2023-07-28

Family

ID=81357590

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011115929.0A Active CN114436303B (en) 2020-10-19 2020-10-19 Macroporous alumina and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114436303B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120919972B (en) * 2025-10-13 2025-12-23 临朐恒辉新材料有限公司 Preparation process of dual mesoporous alumina carrier

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4019978A (en) * 1972-08-29 1977-04-26 Laporte Industries Limited Process for the production of alumina
US4154812A (en) * 1977-03-25 1979-05-15 W. R. Grace & Co. Process for preparing alumina
CN101591555A (en) * 2008-05-28 2009-12-02 北京三聚环保新材料股份有限公司 A kind of organic sulfur desulfurizer and preparation method thereof
CN102039195A (en) * 2009-10-16 2011-05-04 中国石油化工股份有限公司 Preparation method of alumina carrier
CN102730724A (en) * 2012-05-31 2012-10-17 江苏晶晶新材料有限公司 Preparation process for large pore volume and light bulk density activated alumina
CN103100426A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Preparation method of alumina carrier
CN103285844A (en) * 2013-06-28 2013-09-11 福建农林大学 A method for synthesizing mesoporous TiO2 photocatalyst using lignin as template
CN103801346A (en) * 2012-11-08 2014-05-21 中国石油化工股份有限公司 Preparation method for hydrotreatment catalyst
CN104118894A (en) * 2014-08-15 2014-10-29 福州大学 Preparation method of aluminum oxide centralized in pore diameter distribution
CN104556164A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Macroporous alumina and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105363446B (en) * 2014-08-25 2019-06-14 中国石油化工股份有限公司 A kind of naphtha reforming catalyst and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4019978A (en) * 1972-08-29 1977-04-26 Laporte Industries Limited Process for the production of alumina
US4154812A (en) * 1977-03-25 1979-05-15 W. R. Grace & Co. Process for preparing alumina
CN101591555A (en) * 2008-05-28 2009-12-02 北京三聚环保新材料股份有限公司 A kind of organic sulfur desulfurizer and preparation method thereof
CN102039195A (en) * 2009-10-16 2011-05-04 中国石油化工股份有限公司 Preparation method of alumina carrier
CN103100426A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Preparation method of alumina carrier
CN102730724A (en) * 2012-05-31 2012-10-17 江苏晶晶新材料有限公司 Preparation process for large pore volume and light bulk density activated alumina
CN103801346A (en) * 2012-11-08 2014-05-21 中国石油化工股份有限公司 Preparation method for hydrotreatment catalyst
CN103285844A (en) * 2013-06-28 2013-09-11 福建农林大学 A method for synthesizing mesoporous TiO2 photocatalyst using lignin as template
CN104556164A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Macroporous alumina and preparation method thereof
CN104118894A (en) * 2014-08-15 2014-10-29 福州大学 Preparation method of aluminum oxide centralized in pore diameter distribution

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
大孔体积低密度活性氧化铝的制备与表征;李国印;支建平;张玉林;;石油炼制与化工(第05期);第28-33页 *
活性氧化铝孔结构的控制;李国印;支建平;张玉林;;无机化学学报(第04期);第563-568页 *

Also Published As

Publication number Publication date
CN114436303A (en) 2022-05-06

Similar Documents

Publication Publication Date Title
CN108855024B (en) A kind of preparation method of alumina carrier with large pore size and high mechanical strength
CN102441437A (en) Preparation method of macroporous alumina carrier and hydrodemetallization catalyst
CN102039203B (en) Hydrotreating catalyst and preparation method thereof
CN107252688A (en) A kind of DCPD hydrogenation of petroleum resin catalyst and its preparation method and application
CN100522349C (en) Novel gamma aluminium oxide catalyst and producing technology
CN114436303B (en) Macroporous alumina and preparation method and application thereof
CN111592023A (en) Preparation method of boron-containing pseudo-boehmite
CN103803615A (en) Preparation method for alumina dry gel
CN103801346B (en) A kind of method preparing hydrotreating catalyst
US4097413A (en) Desulfurization process and catalyst
US4179410A (en) Cobalt-molybdenum-alumina desulfurization catalyst
CN103801312A (en) Preparation method for hydrotreatment catalyst
CN114130379B (en) Preparation method of alumina carrier, alumina carrier prepared by preparation method and application of alumina carrier
CN102451699A (en) Preparation method of hydrotreating catalyst
CN103769124B (en) The preparation method of hydrotreating catalyst
CN112717964B (en) Paraffin hydrofining catalyst and preparation method and application thereof
CN111375428A (en) Process for preparing sulfurized hydrogenation catalyst
CN106925286A (en) Hierarchical and directional preparation method of hydrodemetallization catalyst for deasphalted oil
CN113101967B (en) C5 and/or C9 petroleum resin two-stage hydrofining catalyst and preparation method and application thereof
CN112718013A (en) Alumina carrier and preparation and application thereof
CN114471593B (en) Preparation method of hydrofining catalyst
CN108452839A (en) A kind of Jie's mesoporous-microporous composite molecular sieve, catalyst and its preparation method and application
CN119016077B (en) A heavy oil hydrogenation catalyst, its preparation method and application
CN119098226B (en) A method for preparing a diesel hydrorefining catalyst
CN107029732B (en) A kind of raffinate oil hydrogenation catalysts and preparation method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20231228

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: CHINA PETROLEUM & CHEMICAL Corp.

Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.

TR01 Transfer of patent right