CN113976124A - Hydrofining catalyst and preparation method thereof - Google Patents

Hydrofining catalyst and preparation method thereof Download PDF

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CN113976124A
CN113976124A CN202111386883.0A CN202111386883A CN113976124A CN 113976124 A CN113976124 A CN 113976124A CN 202111386883 A CN202111386883 A CN 202111386883A CN 113976124 A CN113976124 A CN 113976124A
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catalyst
metal
precursor
drying
producing
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CN113976124B (en
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王美玲
徐景东
马小波
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—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
    • B01J23/78—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 alkali- or alkaline earth metals
    • 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
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention belongs to the technical field of hydrofining catalysts, and particularly relates to a hydrofining catalyst with excellent hydrodesulfurization capability. The hydrorefining catalyst consists of active metal, inorganic assistant, organic assistant and carrier, and the active metal component consists of VIB-family and VIII-family metals. The catalyst part II group metal and VIII group metal prepared by the method exist in the form of phyllosilicate phase, so that the two metal parts are anchored in the catalyst bulk phase, and the service life of the catalyst is prolonged. Meanwhile, the catalyst prepared by the method contains VIII group metal, has better dispersity and shows excellent hydrogenation saturation capacity. In addition, because the VIII group metal in the catalyst precursor is anchored in the catalyst bulk phase, when the catalyst is vulcanized, the VIII group metal can be vulcanized after delay to form more hydrodesulfurization and hydrodenitrogenation intrinsic active sites, so that the catalyst also shows better hydrodesulfurization capability.

Description

Hydrofining catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of hydrofining catalysts, and particularly relates to a hydrofining catalyst with excellent hydrodesulfurization capability.
Background
Nowadays, environmental regulations are becoming stricter, and the requirement for cleanliness of fuel oil is also becoming higher and higher. The main means for cleaning the oil product is hydrofining, which aims to remove substances such as sulfur, nitrogen, aromatic hydrocarbon, olefin, metal and the like in the oil product and produce the fuel oil meeting the standard. The core technology in the hydrofining technology is the development of hydrofining catalysts. The development of a hydrofining catalyst with more excellent performance not only can enable a hydrogenation device to produce oil products meeting the standard, but also can enable a refinery to save energy and reduce cost.
For fuel oils, especially diesel oil (containing benzothiophenes), the major difficulties in refining are the deep removal of sulfides and the deep hydrogenation saturation of polycyclic aromatic hydrocarbons. According to the existing research (Journal of Catalysis,2007,249(2):220-2And (4) clustering. However, in the case of catalysts prepared by a general method, Ni or Co is preferentially sulfided during sulfidation, and thus modification of MoS cannot be achieved2The purpose of clustering results in a limited number of intrinsic active sites of the catalyst, which leads to a reduction in desulfurization activity. In the prior art, US 6280610B1 discloses a process for preparing a hydrorefining catalyst comprising a group viii hydrogenation metal and a group vib hydrogenation metal in the form of their oxides, which catalyst is calcined by conventional impregnation and the resulting catalyst is then calcined by impregnationOrganic compound containing 2 hydroxyl groups and 2-10 carbon atoms is used as additive, and the final catalyst is obtained without roasting. The catalyst directly performs hydrodesulfurization without vulcanization and has hydrodesulfurization activity, and the hydrodesulfurization activity is better after vulcanization. Researches show that the addition of the complexing agent can delay the vulcanization of the VIII metal and increase the vulcanization temperature, so that more intrinsic desulfurization active sites are generated. However, the catalyst prepared by the method has the defect of low hydrogenation saturation capacity. Chinese patent CN 106362782 a discloses a preparation method of a hydrorefining catalyst. The catalyst contains a carrier and VIII family metal, VIB family metal and auxiliary agent phosphorus or combined auxiliary agent phosphorus and magnesium loaded on the carrier. The catalyst support is made from a modified hydrated alumina. Compared with the prior art, the catalyst has better hydrodesulfurization and hydrodenitrogenation activities. However, the catalyst has a narrow pore size, and the hydrocarbon molecules cannot diffuse smoothly in the catalyst, and the use of middle distillate feedstocks with a wide boiling range is limited. Chinese patent CN 106455736B discloses a catalyst for hydrotreating hydrocarbon oil. The catalyst comprises 10-40% VIB group metal oxide and 0.5-15% VIII group metal oxide, and organic additive with 0.05-3 times of total metal element mole number. The catalyst support is comprised of a group IIA metal modified silica-alumina. The catalyst shows slightly excellent hydrogenation activity and can also treat middle distillate oil with wide boiling point range, but the activity of the catalyst is found to be reduced rapidly through research, so that the service life of the catalyst is shorter.
The hydrofining catalyst in the prior art can only show good catalytic performance in one or two aspects of desulfurization activity capability, hydrogenation saturation capability, raw material adaptability, catalyst service life and the like, but can not simultaneously show good catalytic performance in multiple aspects.
Disclosure of Invention
The invention aims to provide a hydrofining catalyst and a preparation method thereof. The catalyst prepared by the method can anchor partial VIII group metal or IIA group metal in a catalyst bulk phase, so that the aggregation and growth of the metals in the hydrogenation process are limited, and the service life of the catalyst is prolonged. Meanwhile, the catalyst prepared by the method contains VIII group metal, has better dispersity and shows excellent hydrogenation saturation capacity. In addition, because the VIII group metal in the catalyst precursor is anchored in the catalyst bulk phase, when the catalyst is vulcanized, the VIII group metal can be vulcanized after delay to form more hydrodesulfurization and hydrodenitrogenation intrinsic active sites, so that the catalyst also shows better hydrodesulfurization capability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the hydrorefining catalyst consists of an active metal compound, an inorganic assistant, an organic assistant and a carrier, wherein the active metal component consists of metals in VIB group and VIII group. Comprises the following components in percentage by weight:
(1)20-40 wt% of an active metal compound, wherein the active metal is selected from one or more of a group VIB metal and a group VIII metal; preferably, the group VIB metal is molybdenum or tungsten and the group VIII metal is nickel or cobalt;
(2)3-15 wt% of inorganic auxiliary agent selected from one or more of phosphorus, titanium, magnesium or boron;
(3)0.1-8 wt% of organic auxiliary agent selected from one or more of glycerol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, citric acid, tartaric acid, glucose, ethylenediamine and ethylenediamine tetraacetic acid;
(4)50-70 wt% of the catalyst component consists of at least one of alumina, silica or silica alumina;
(5)0.1-10 wt% of the catalyst component is composed of phyllosilicate, [ Ni ]x Mg1-x]3Si2O5(OH)4Composition is carried out; x is in the range of 0-1
The sum of the total mass fractions is 100 wt%.
Unless otherwise specified, mass percentages used herein are percentages by weight of the indicated material to weight of the catalyst.
The preparation method of the hydrofining catalyst comprises the following specific steps:
(1) mixing and stirring a metal precursor salt solution, a silicon-containing compound precursor and water to form a slurry;
(2) adding a certain amount of ammonia water into the slurry obtained in the step (1), and stirring the obtained mixed solution at room temperature for a certain time;
(3) stirring the slurry prepared in the step (2) at a certain temperature to carry out ammonia distillation reaction;
(4) carrying out hydrothermal reaction on the mixture obtained in the step (3) for a certain time;
(5) filtering, washing and drying the solid-liquid mixture obtained in the step (4) to obtain an oxide precursor;
(6) roasting the oxide precursor obtained in the step (5), kneading, molding, drying and roasting for the second time;
(7) and (3) impregnating the precursor formed by the catalyst obtained in the step (6) with a metal impregnation liquid containing at least one organic additive, and drying to obtain the final catalyst.
The metal precursor salt in the step (1) is IIA metal precursor salt and/or VIII metal precursor salt; wherein the metal precursor salt form comprises one or more of oxide, chloride, hydroxide, nitrate, carbonate, sulfate and organic acid salt;
preferably, the metal in the IIA metal precursor salt is one or two of Mg and Ca, and the metal in the VIII metal precursor salt is one or two of Co and Ni;
more preferably, the metal precursor salt is a precursor salt of one or both of Mg and Ni.
Preferably, the total mass fraction of the metal precursor salt converted into oxide used in the step (1) accounts for 2-15 wt% of the total mass of the catalyst, and the preferred total mass fraction of the metal oxide is 5-10 wt%;
in the step (1), the silicon-containing compound precursor is one or more of water glass, sodium silicate, silicon oxide, silica sol, amorphous silica-alumina, a silica-alumina molecular sieve and a silicon dioxide-alumina mixture;
preferably, the silicon-containing compound precursor is one of amorphous silica-alumina, a silica-alumina molecular sieve, a silica-alumina mixture.
Preferably, the total mass fraction of the oxides converted from the silicide accounts for 50-80 wt% of the total mass of the catalyst; preferably, the total mass fraction of the silicide-containing material converted into the oxide is 60-70 wt%;
preferably, the silicon-containing compound of step (1), after conversion to silica, is present in the oxide
2-15 wt% of alumina in balance; preferably, the silica is present in the oxide in an amount of 5 to 10 wt%.
Preferably, the concentration and the dosage of the ammonia water used in the step (2) are not particularly required, and the pH value of the mixed solution in the step (2) needs to be adjusted to 11-13;
preferably, the stirring time in the step (2) is 3-24 hours, preferably 10-15 hours;
preferably, the ammonia distillation reaction temperature in the step (3) is 70-90 ℃, more preferably 80-85 ℃, and the ammonia distillation time is not fixed until the pH value of the mixed solution is 7-8;
preferably, the hydrothermal conditions in step (4) are: the hydrothermal temperature in the closed container is 120-230 ℃, and more preferably 160-200 ℃; the hydrothermal time is 12-48 h, preferably 24-36 h;
preferably, in the step (5), the solid-liquid mixture obtained in the step (4) is cooled to room temperature; washing with deionized water until the pH value of the filtrate is 6-8; the drying condition is vacuum drying, forced air drying or other heat transfer drying, and the temperature is preferably 80-120 ℃; the drying time is 6-18 h, preferably 10-14 h;
the atmosphere in which the oxide precursor is calcined in step (6) is air, an inert atmosphere, or an atmosphere having a reducing property (CO, H)2、CO+N2、H2+N2Etc.); preferably, the calcination atmosphere of the catalyst precursor is CO + N2Or H2+N2Reducing the components CO and H in a reducing atmosphere2The proportion of the organic silicon compound is 5-20% by volume; the roasting temperature is 300-600 ℃, and preferably 400-500 ℃; the roasting time is 1-5 h, preferably 2-3 h;
the catalyst precursor forming conditions in the step (6) are as follows: uniformly mixing the roasted catalyst precursor and the sesbania powder serving as a pore-forming agent according to the proportion of 90: 1-20: 1 mass ratio; then adding 1-5 mass% nitric acid aqueous solution for kneading, wherein the mass ratio of the solution to the catalyst precursor powder is 0.8-1.2; extruding and molding the wet mixture obtained by kneading to obtain a strip-shaped extrudate;
drying for 8-15 h at 80-120 ℃ in air under the drying condition in the step (6); roasting for the second time at 400-900 ℃ for 2-6 h in air or inert atmosphere; preferably, the roasting temperature is 600-800 ℃ and roasting is carried out for 2-6 h;
the impregnation liquid in the step (7) contains at least one of group VIII metal and group VIB metal, preferably, the group VIII metal is Ni or Co, and the group VIB metal is Mo;
the impregnation liquid in the step (7) contains at least one of inorganic additives P or B;
the impregnation liquid in the step (7) contains at least one organic auxiliary agent, and the organic auxiliary agent is one or more of glycerol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, citric acid, tartaric acid, glucose, ethylenediamine and ethylenediamine tetraacetic acid;
the drying mode in the step (7) is air and inert atmosphere (N)2、He、Ar、CO2Low oxygen atmosphere), conductive heat drying, or the like; the drying temperature is 30-250 ℃, preferably 100-200 ℃; the drying time is 1-18 h, preferably 2-5 h;
in the present invention, the group II metal Mg and the group VIII metal Ni in the oxide precursor after the hydrothermal drying can form phyllosilicate phase with silicide, namely [ Nix Mg1-x]3Si 2O5(OH)4The unit structure of the material is composed of Si-O tetrahedron, Ni-O octahedron and Mg-O octahedron. Preferably, the amount of the phyllosilicate phase is 2 to 20% by mass of the oxide precursor obtained in step (5). After the oxide precursor is calcined in a reducing atmosphere, Ni and Mg in the oxide precursor are partially reduced to form Ni0And Mg0Is present in part in the form of [ Ni ]x Mg1-x]3Si 2O5(OH)4Is present in the bulk phase with the catalyst precursor. Part of Ni and Mg exist in the form of NiO and MgO after the catalyst precursor is formed and roasted, and part of Ni and Mg still exist in the form of [ NixMg1-x]3Si 2O5(OH)4Exist in the form of (1).
The physical properties of the catalyst of the invention are as follows: the specific surface area is 50-250 m2A specific surface area of 100 to 200 m/g2(ii)/g; the pore volume is 0.2-0.6 mL/g, preferably 0.3-0.5 mL/g; the average pore diameter is 7-18 nm, preferably 10-15 nm.
The invention has the following remarkable advantages:
the invention provides a preparation method of a novel hydrofining catalyst. The catalyst part II group metal and VIII group metal prepared by the method exist in the form of phyllosilicate phase, so that the two metal parts are anchored in the catalyst bulk phase, are not easy to aggregate and grow in the reaction process, and have better dispersibility. During the vulcanization process of the catalyst, the VIII group metal anchored in the bulk phase is more difficult to be vulcanized, so that the vulcanization time is delayed, and MoS can be modified2More hydrodesulfurization active sites are formed at the edges of the platelets, and good catalytic activity is shown in the hydrofining of the middle distillate oil. The catalyst provided by the invention shows excellent desulfurization performance and aromatic hydrocarbon saturation capacity on diesel oil hydrodesulfurization, and the relative desulfurization activity of the catalyst is up to 131%.
Drawings
Fig. 1 is an SEM image of the catalyst precursor of example 1.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
The preparation method and application of the present invention are further described with reference to the following specific examples, but the specific embodiments described herein are only for illustrating and explaining the present invention and are not intended to limit the present invention.
Example 1
Weighing 7.78g of nickel nitrate hexahydrate, 12.72g of magnesium nitrate hexahydrate, 12.5g of silica sol (containing 40wt% of silicon dioxide), 80g of pseudo-boehmite powder and 500mL of deionized water, mixing, finally adding 40mL of ammonia water (the mass concentration is 25-28%), and carrying out reaction on the mixture in a chamberStirring for 12h, heating the mixed solution to 80 ℃ after stirring is finished, and carrying out ammonia distillation reaction until the pH value of the mixed solution is reduced to 7. And transferring the mixed solution into a hydrothermal kettle, heating to 200 ℃, carrying out hydrothermal treatment for 24 hours, taking out, and cooling to room temperature. Filtering, washing the filter cake with deionized water for 3 times, drying in a vacuum drying oven at 80 ℃ for 12H, and introducing 5 vol% H in a tubular furnace2+95vol％N2The mixed gas is roasted for 2 hours at the temperature of 450 ℃ to obtain the catalyst precursor powder.
The catalyst precursor is of a layered structure, and an electron microscope is shown in figure 1.
Weighing 100g of precursor powder and 3g of sesbania powder, and uniformly mixing for 0.5 h; weighing 2g of 68 wt% nitric acid, diluting the nitric acid into 100g of deionized water, slowly adding the nitric acid into the mixed powder within 3min, and kneading for 20 min; extruding the obtained wet block-shaped object by using a clover die with the specification of 1.59 x 1.45mm for molding; placing the formed wet precursor in air at room temperature for 2h, and drying in a forced air drying oven at 120 ℃ for 12 h; and roasting the dried precursor in a muffle furnace at 600 ℃ for 4h to obtain a formed catalyst precursor.
70g of the formed catalyst precursor is weighed and dipped in dipping solution containing Ni, Mo, P and glycol in equal volume, wherein the dipping solution contains 4.2 wt% of Ni, 26.2 wt% of Mo, 4.7 wt% of P and 8wt% of glycol, and the balance is mainly deionized water and acid radical ions combined with metal ions or auxiliary elements. After the impregnated catalyst is cured for 2 hours at room temperature, the catalyst is dried for 2 hours in a forced air drying oven at 140 ℃ to obtain the final hydrofining catalyst Ni2-Mg2-PL。
Example 2
1.95g of nickel nitrate hexahydrate, 12.72g of magnesium nitrate hexahydrate, 12.5g of silica sol (containing 40wt% of silica), 80g of pseudo-boehmite powder and 500mL of deionized water were weighed and mixed, followed by addition of 40mL of ammonia water (mass concentration of 25-28%). And stirring the mixture at room temperature for 12 hours, and after stirring, heating the mixed solution to 80 ℃ to carry out ammonia distillation reaction until the pH value of the mixed solution is reduced to 7. And transferring the mixed solution into a hydrothermal kettle, heating to 200 ℃, carrying out hydrothermal treatment for 24 hours, taking out, and cooling to room temperature. Filtering, washing the filter cake with deionized water for 3 times, and drying at 80 deg.C in a vacuum drying ovenDrying for 12H, then placing in a tube furnace and introducing 5 vol% H2+95vol％N2The mixer is roasted for 2h at the temperature of 450 ℃ to obtain catalyst precursor powder.
The molding conditions were the same as in example 1.
70g of the formed catalyst precursor is weighed and dipped in dipping solution containing Ni, Mo, P and glycol in equal volume, wherein the dipping solution contains 7 wt% of Ni, 26.2 wt% of Mo, 4.7 wt% of P and 8wt% of glycol, and the balance is mainly deionized water and acid radical ions combined with metal ions or auxiliary elements. After the impregnated catalyst is cured for 2 hours at room temperature, the catalyst is dried for 2 hours in a forced air drying oven at 140 ℃ to obtain the final hydrofining catalyst Ni0.5-Mg2-PL。
Example 3
Weighing 7.78g of nickel nitrate hexahydrate, 3.18g of magnesium nitrate hexahydrate, 12.5g of silica sol (containing 40wt% of silicon dioxide), 80g of pseudo-boehmite powder and 500mL of deionized water, and then adding 40mL of ammonia water (with the mass concentration of 25-28%). And stirring the mixture at room temperature for 12 hours, and after stirring, heating the mixed solution to 80 ℃ to carry out ammonia distillation reaction until the pH value of the mixed solution is reduced to 7. And transferring the mixed solution into a hydrothermal kettle, heating to 200 ℃, carrying out hydrothermal treatment for 24 hours, taking out, and cooling to room temperature. Then filtering, washing the filter cake with deionized water for 3 times, placing the filter cake in a vacuum drying oven for drying at 80 ℃ for 12H, and then placing the filter cake in a tubular furnace for introducing 5 vol% H2+95vol％N2The mixer is roasted for 2h at the temperature of 450 ℃ to obtain catalyst precursor powder.
The molding conditions were the same as in example 1.
70g of the formed catalyst precursor is weighed and dipped in a dipping solution containing Ni, Mo, Mg, P and glycol in equal volume, wherein the dipping solution contains 4.2 wt% of Ni, 26.2 wt% of Mo, 2.2 wt% of Mg, 4.7 wt% of P and 8wt% of glycol, and the balance is mainly deionized water and acid radical ions combined with metal ions or auxiliary elements. After the impregnated catalyst is cured for 2 hours at room temperature, the catalyst is dried for 2 hours in a forced air drying oven at 140 ℃ to obtain the final hydrofining catalyst Ni2-Mg0.5-PL。
Example 4
3.89g of nickel nitrate hexahydrate and 12.72g of magnesium nitrate hexahydrate are weighed,12.5g of silica sol (containing 40wt% of silica), 80g of pseudo-boehmite powder and 500mL of deionized water were mixed, and then 40mL of ammonia water (with a mass concentration of 25-28%) was added. And stirring the mixture at room temperature for 12 hours, and after stirring, heating the mixed solution to 80 ℃ to carry out ammonia distillation reaction until the pH value of the mixed solution is reduced to 7. And transferring the mixed solution into a hydrothermal kettle, heating to 200 ℃, carrying out hydrothermal treatment for 24 hours, taking out, and cooling to room temperature. Then filtering, washing the filter cake with deionized water for 3 times, placing the filter cake in a vacuum drying oven for drying at 80 ℃ for 12H, and then placing the filter cake in a tubular furnace for introducing 5 vol% H2+95vol％N2The mixer is roasted for 2h at the temperature of 450 ℃ to obtain catalyst precursor powder.
The molding conditions were the same as in example 1.
70g of the formed catalyst precursor is weighed and dipped in dipping solution containing Ni, Mo, P and glycol in equal volume, wherein the dipping solution contains 5.6 wt% of Ni, 26.2 wt% of Mo, 4.7 wt% of P and 8wt% of glycol, and the balance is mainly deionized water and acid radical ions combined with metal ions or auxiliary elements. After the impregnated catalyst is cured for 2 hours at room temperature, the catalyst is dried for 2 hours in a forced air drying oven at 140 ℃ to obtain the final hydrofining catalyst Ni1-Mg2-PL。
Example 5
Weighing 7.78g of nickel nitrate hexahydrate, 6.36g of magnesium nitrate hexahydrate, 12.5g of silica sol (containing 40wt% of silicon dioxide), 80g of pseudo-boehmite powder and 500mL of deionized water, and then adding 40mL of ammonia water (with the mass concentration of 25-28%). And stirring the mixture at room temperature for 12 hours, and after stirring, heating the mixed solution to 80 ℃ to carry out ammonia distillation reaction until the pH value of the mixed solution is reduced to 7. And transferring the mixed solution into a hydrothermal kettle, heating to 200 ℃, carrying out hydrothermal treatment for 24 hours, taking out, and cooling to room temperature. Then filtering, washing the filter cake with deionized water for 3 times, placing the filter cake in a vacuum drying oven for drying at 80 ℃ for 12H, and then placing the filter cake in a tubular furnace for introducing 5 vol% H2+95vol％N2The mixer is roasted for 2h at the temperature of 450 ℃ to obtain catalyst precursor powder.
The molding conditions were the same as in example 1.
Weighing 70g of the precursor of the formed catalyst, and soaking the precursor in soaking solution containing Ni, Mo, Mg, P and glycol in equal volume, wherein the soaking solution contains 5.6wt% Ni, 26.2 wt% Mo, 1.1 wt% Mg, 4.7 wt% P and 8wt% ethylene glycol, the balance being mainly deionized water and acid ions combined with metal ions or auxiliary elements. After the impregnated catalyst is cured for 2 hours at room temperature, the catalyst is dried for 2 hours in a forced air drying oven at 140 ℃ to obtain the final hydrofining catalyst Ni2-Mg1-PL。
Comparative example 1
12.5g of silica sol (containing 40wt% of silica), 80g of pseudo-boehmite powder and 500mL of deionized water were weighed and mixed, followed by addition of 40mL of ammonia water (25-28% by mass). And stirring the mixture at room temperature for 12 hours, and after stirring, heating the mixed solution to 80 ℃ to carry out ammonia distillation reaction until the pH value of the mixed solution is reduced to 7. And transferring the mixed solution into a hydrothermal kettle, heating to 200 ℃, carrying out hydrothermal treatment for 24 hours, taking out, and cooling to room temperature. Then filtering, washing the filter cake with deionized water for 3 times, placing the filter cake in a vacuum drying oven for drying at 80 ℃ for 12H, and then placing the filter cake in a tubular furnace for introducing 5 vol% H2+95vol％N2The mixer is roasted for 2h at the temperature of 450 ℃ to obtain catalyst precursor powder.
The molding conditions were the same as in example 1.
70g of the formed catalyst precursor is weighed and dipped with a dipping solution containing Ni, Mo, Mg, P and glycol in equal volume, wherein the dipping solution contains 7 wt% of Ni, 26.2 wt% of Mo, 2.2 wt% of Mg, 4.7 wt% of P and 8wt% of glycol, and the balance is mainly deionized water and acid radical ions combined with metal ions or auxiliary elements. After the impregnated catalyst is cured for 2 hours at room temperature, the catalyst is dried for 2 hours in a forced air drying oven at 140 ℃ to obtain the final comparative catalyst N-PL.
The physicochemical properties of the above catalyst are shown in Table 1.
TABLE 1 physical Properties of the catalysts prepared
Figure BDA0003367382470000091
And (3) hydrogenation activity test:
in a high-pressure fixed bed reactor, the catalyst is used for evaluating the deep desulfurization performance of diesel oil. The properties of the feed diesel are shown in Table 2. 20mL of catalyst and 30mL of quartzAfter sand is mixed and filled, the catalyst is vulcanized by adopting a wet method in the device. The evaluation conditions of the relative desulfurization activity of the catalyst are as follows: the reaction temperature is 350 ℃, the pressure of the reaction hydrogen is 4MPa, and the hourly space velocity of the reaction liquid is 1.5h-1The hydrogen-oil ratio was 300, and a sample was taken after 100 hours of reaction. The aromatic content was calculated by GC-MS analysis of the middle distillate oil family composition. The sulfur content in the raw oil is measured by an X fluorescence sulfur detector and the sulfur content in each product oil is measured by a chemiluminescence sulfur detector. And the relative desulfurization activity was calculated according to the following formula.
Figure BDA0003367382470000092
Wherein S isfThe sulfur content (percentage) of raw oil; spSulfur content of the resulting oil hydrofinished for the example catalyst; sprComparative example 1 catalyst produced oil sulfur content.
The hydrodesulfurization activity and the aromatics saturation activity are compared in Table 3.
TABLE 2 raw diesel properties
Figure BDA0003367382470000101
TABLE 3 comparison of catalyst hydrodesulfurization activities
Catalyst and process for preparing same Relative desulfurization activity% Aromatic content of the product%
Example 1 Ni2-Mg2-PL 131 28
Example 2 Ni0.5-Mg2-PL 109 33
Example 3/Ni2-Mg0.5-PL 121 30.4
Example 4 Ni1-Mg2-PL 115 31.1
Example 5 Ni2-Mg1-PL 127 29.5
Comparative example 1/N-PL 100 35
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (10)

1. A hydrorefining catalyst characterized by: the catalyst component comprises an active metal compound, an inorganic auxiliary agent, an organic auxiliary agent and a carrier; comprises the following components in percentage by weight:
(1)20-40 wt% of an active metal compound, wherein the active metal is selected from one or more of a group VIB metal and a group VIII metal;
(2)3-15 wt% of inorganic auxiliary agent selected from one or more of phosphorus, titanium, magnesium or boron;
(3)0.1-8 wt% of organic auxiliary agent;
(4)50-70 wt% of a carrier component;
(5)0.1 to 10wt% of a phyllosilicate component;
the sum of the total mass fractions is 100 wt%.
2. A hydrofinishing catalyst according to claim 1, wherein: the VIB group metal is molybdenum or tungsten, and the VIII group metal is nickel or cobalt; the organic auxiliary agent is selected from one or more of glycerol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, citric acid, tartaric acid, glucose, ethylenediamine and ethylenediamine tetraacetic acid; the carrier component is composed of at least one of alumina, silicon oxide or silicon-aluminum oxide; the phyllosilicate being [ Nix Mg1-x ]3Si2O5 (OH)4And x ranges from 0 to 1.
3. The process for producing a hydrorefining catalyst according to any of claims 1 to 2, characterized by:
the method comprises the following steps:
(1) mixing and stirring a metal precursor salt solution, a silicon-containing compound precursor and water to form a slurry;
(2) adding a certain amount of ammonia water into the slurry obtained in the step (1), and stirring the obtained mixed solution at room temperature for a certain time;
(3) stirring the slurry prepared in the step (2) at a certain temperature to carry out ammonia distillation reaction;
(4) carrying out hydrothermal reaction on the mixture obtained in the step (3) for a certain time;
(5) filtering, washing and drying the solid-liquid mixture obtained in the step (4) to obtain an oxide precursor;
(6) roasting the oxide precursor obtained in the step (5), kneading, molding, drying and roasting for the second time;
(7) and (3) impregnating the precursor formed by the catalyst obtained in the step (6) with a metal impregnation liquid containing at least one organic additive, and drying to obtain the final catalyst.
4. The method of producing a hydrorefining catalyst according to claim 3, characterized in that:
the metal precursor salt in the step (1) is IIA metal precursor salt and/or VIII metal precursor salt; wherein the metal precursor salt form comprises one or more of oxide, chloride, hydroxide, nitrate, carbonate, sulfate and organic acid salt; the total mass fraction of the oxides converted from the metal precursor salt used in the step (1) accounts for 2-15 wt% of the total mass of the catalyst; in the step (1), the silicon-containing compound precursor is one or more of water glass, sodium silicate, silicon oxide, silica sol, amorphous silica-alumina, a silica-alumina molecular sieve and a silicon dioxide-alumina mixture; the total mass fraction of the oxides converted from the silicide is 50-80 wt% of the total mass of the catalyst.
5. The method of producing a hydrorefining catalyst according to claim 3, characterized in that:
adding the ammonia water used in the step (2) until the pH value of the mixed solution in the step (2) is adjusted to 11-13; the stirring time in the step (2) is 3-24 h.
6. The method of producing a hydrorefining catalyst according to claim 3, characterized in that: in the step (3), the ammonia distillation reaction temperature is 70-90 ℃, and ammonia distillation is carried out until the pH of the mixed solution is = 7-8; the hydrothermal conditions in the step (4) are as follows: the hydrothermal temperature in the closed container is 120-230 ℃, and the hydrothermal time is 12-48 h.
7. The method of producing a hydrorefining catalyst according to claim 3, characterized in that:
in the step (5), cooling the solid-liquid mixture obtained in the step (4) to room temperature; washing is carried out by washing with deionized water until the pH of the filtrate is = 6-8, and the drying temperature is 80-120 ℃; the drying time is 6-18 h.
8. The method of producing a hydrorefining catalyst according to claim 3, characterized in that:
the oxide precursor firing atmosphere in the step (6) is any one of air, an inert atmosphere, or an atmosphere having a reducing property; the roasting temperature is 300-600 ℃, and the roasting time is 1-5 h.
9. The method of producing a hydrorefining catalyst according to claim 3, characterized in that:
the catalyst precursor forming conditions in the step (6) are as follows: uniformly mixing the roasted catalyst precursor and the sesbania powder serving as a pore-forming agent according to the proportion of 90: 1-20: 1 mass ratio; then adding 1-5 mass% nitric acid aqueous solution for kneading, wherein the mass ratio of the solution to the catalyst precursor powder is 0.8-1.2; extruding and molding the wet mixture obtained by kneading to obtain a strip-shaped extrudate; drying for 8-15 h at 80-120 ℃ in air under the drying condition in the step (6); the second roasting condition is roasting for 2-6 h at 400-900 ℃ in air or inert atmosphere.
10. The method of producing a hydrorefining catalyst according to claim 3, characterized in that:
the impregnating solution in the step (7) contains at least one metal of VIII group and VIB group; the impregnation liquid in the step (7) contains at least one of inorganic additives P or B; the impregnation liquid comprises at least one organic auxiliary agent; the drying temperature is 30-250 ℃, and the drying time is 1-18 h.
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JP2002126539A (en) * 2000-10-18 2002-05-08 Tonengeneral Sekiyu Kk Production method of catalyst for hydrogenation treatment
CN1488716A (en) * 2002-10-10 2004-04-14 中国石油化工股份有限公司 Hydroprocessing catalyst and preparing method thereof
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