CN114453005A - Hydrofining catalyst and preparation method and application thereof - Google Patents

Hydrofining catalyst and preparation method and application thereof Download PDF

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CN114453005A
CN114453005A CN202011134765.6A CN202011134765A CN114453005A CN 114453005 A CN114453005 A CN 114453005A CN 202011134765 A CN202011134765 A CN 202011134765A CN 114453005 A CN114453005 A CN 114453005A
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catalyst
content
molecular sieve
sba
alumina
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CN114453005B (en
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杨占林
唐兆吉
杜艳泽
樊宏飞
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • B01J35/66—Pore distribution
    • B01J35/695—Pore distribution polymodal
    • 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
    • C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • 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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Abstract

The invention discloses a hydrofining catalyst and a preparation method and application thereof. The hydrofining catalyst comprises: the catalyst comprises a carrier, an active metal component, nano magnesium oxide and an organic auxiliary agent, wherein the carrier comprises an Al-SBA-15 molecular sieve and aluminum oxide. The hydrofining catalyst can deeply remove nitrogen-containing compounds in shale oil, has good hydrogenation performance, meets the quality requirement of subsequent process production, and ensures that the service performance of the cracking catalyst is fully exerted.

Description

Hydrofining catalyst and preparation method and application thereof
Technical Field
The invention relates to a hydrofining catalyst, a preparation method and application thereof, and the catalyst is particularly suitable for a shale oil distillate oil hydrotreating process.
Background
In natural resources, oil shale is mainly generated by low-grade plankton such as algae through decomposition and coalification, like petroleum. Shale oil extracted from oil shale is called as artificial petroleum by methods such as low dry distillation and the like, and can be further processed and refined to prepare liquid fuels such as gasoline, kerosene, diesel oil and the like. The development of the industry is limited because the production process pollutes the environment due to the fact that the technology is not over-closed in the early stage of exploitation of the oil shale. In recent years, with the progress of technology, this problem has been well solved. It is expected that shale oil will play an increasingly important role in energy families under the current situation of shortage of petroleum resources and high price of oil. However, unlike natural petroleum, shale oil contains more unsaturated hydrocarbons and non-hydrocarbon components such as sulfur, nitrogen, oxygen and the like, and the high content of heterocyclic aromatic hydrocarbon in shale oil greatly limits the shale oil to be directly used as transportation fuel oil, and NOx and SOx generated by a large amount of sulfur and nitrogen impurities have adverse effects on the environment.
The shale oil processing method mainly comprises a non-hydrotreating method and a hydrotreating method. Non-hydroprocessing generally includes acid-base refining, solvent refining, adsorption refining, addition of stabilizers, and the like. In the aspect of a hydrotreating method, the American oil refinery company mainly carries out hydrotreating pretreatment on shale oil to remove impurities such as sulfur, nitrogen, arsenic and the like in the shale oil, and then produces various oil products in a refinery according to a conventional processing technology; the Brazil oil refining company divides the shale oil into light and heavy fractions, the light fraction is catalytically cracked to produce gasoline products, and the heavy fraction is used as fuel oil; the australian SPP company hydrofinishes shale oil to produce ultra low sulfur light fuel oil.
The hydrotreating process is to load metal oxide containing VIII and VIB groups in the periodic table into refractory inorganic porous material, generally adopt alumina, silica, titania, silicon carbide, boron oxide, zirconia and composite carriers combined together, prepare catalyst precursor through an impregnation process, and prepare the finished catalyst through drying and roasting steps. The finished catalyst is presulfurized before use, i.e. under the condition of containing hydrogen sulfide, sulfur-containing organic compound or elemental sulfur, the oxidation state catalyst is converted into vulcanization state catalyst, and hydrogenation reaction is carried out.
USP4419218 discloses a method for producing aviation kerosene by hydrocracking demetallized shale oil, wherein a hydrofining agent takes Mo-Ni-P as an active metal component, alumina as a carrier, a hydrocracking catalyst takes Co-Cr-Mo trimetal as an active component, and a ZSM-12 molecular sieve as a carrier, the aviation kerosene yield reaches 70%, but the effect of the refining agent is poor, so that the quality of a cracked product is influenced.
CN1785512A discloses a preparation method of a hydrocarbon cracking catalyst containing ferrous iron, the catalyst is composed of 5-20% of aluminum hydrogen phosphate, 5-15% of ferrous iron and the balance of clay, is suitable for hydrocarbon catalytic cracking reaction of fixed bed high nitrogen shale oil and high wax-containing crude oil in a fixed bed, and has good cracking performance.
CN101590416A discloses a method for preparing a molybdenum-nickel hydrogenation catalyst, which comprises the steps of mixing, kneading and impregnating to prepare the catalyst, firstly adding molybdenum oxide, titanium-containing compound and phosphorus-containing compound into alumina and/or alumina precursor, adding nitric acid solution, mixing, kneading, extruding into strips, drying and calcining to obtain alumina forming material containing titanium, phosphorus and molybdenum, impregnating with phosphoric acid solution containing nickel, drying and calcining to obtain the molybdenum-nickel hydrogenation catalyst, but the catalyst has poor refining effect on distillate oil with high nitrogen content.
CN1052501A discloses a hydrorefining catalyst and a preparation method thereof, the catalyst takes silicon oxide-aluminum oxide as a carrier, adopts three active metal components of W-Mo-Ni and boron auxiliary agent, adopts a sectional impregnation method to impregnate, and obtains a finished product catalyst after drying and roasting, and when the nitrogen content is increased, the denitrification effect is not obvious.
The hydrotreating catalyst prepared by the prior art has low denitrification activity, and particularly has poor denitrification effect when meeting shale oil distillate with high nitrogen content, and directly influences the reaction performance of the catalyst in a subsequent cracking section reactor, thereby influencing the quality of cracked products, shortening the running period of a device and increasing the running cost.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a hydrofining catalyst suitable for processing shale oil and a preparation method and application thereof. The hydrofining catalyst of the invention can deeply remove nitrogen-containing compounds in shale oil, has good hydrogenation performance, meets the quality requirement of subsequent process production, and ensures that the service performance of the cracking catalyst is fully exerted.
In a first aspect, the present invention provides a hydrofinishing catalyst comprising: the catalyst comprises a carrier, an active metal component, nano magnesium oxide and an organic auxiliary agent, wherein the carrier comprises an Al-SBA-15 molecular sieve and aluminum oxide.
Further, the properties of the hydrofinishing catalyst are as follows: the specific surface area is 180-240 m2The pore volume is 0.28-0.45 mL/g, and the content of the medium strong acid accounts for 50-70%, preferably 53-63% of the total acid content.
The active metal component is a metal in a VIII group and a metal in a VIB group, the metal in the VIII group is preferably Co and/or Ni, and the metal in the VIB group is preferably W and/or Mo. Based on the weight of the final hydrofining catalyst, the content of the VIII family metal calculated by oxide is 1wt% -15 wt%, preferably 3wt% -10 wt%, and the content of the VIB family metal calculated by oxide is 10wt% -30 wt%, preferably 15wt% -25 wt%.
Further, in the hydrofining catalyst, the content of the carrier is 60-74% by weight of the catalyst, the content of the active metal component is 11-31% by weight of the oxide, and the content of the nano magnesium oxide is 1-6%.
Furthermore, in the hydrofining catalyst, the mole ratio of the content of the organic auxiliary agent to the VIB-group metal atom is 0.01: 1-12: 1, preferably 0.01: 1-10: 1.
further, the organic auxiliary agent is one or a combination of more of ribitol, D-mannitol and stachyose.
Furthermore, in the carrier, the weight content of the Al-SBA-15 molecular sieve is 2-20%, preferably 3-12%, and the weight content of the alumina is 80-98%, preferably 88-97%.
Further, the pore distribution of the Al-SBA-15 molecular sieve comprises: the pore volume occupied by pores with a pore diameter <4nm is less than 20%, preferably less than 15% of the total pore volume; in the Al-SBA-15 molecular sieve, the ratio of B acid to L acid is below 1.
Furthermore, the ratio of B acid to L acid in the Al-SBA-15 molecular sieve can be less than 0.8, less than 0.5 and less than 0.4. The ratio of the B acid to the L acid in the molecular sieve can be more than 0.1, and can also be more than 0.2.
Furthermore, in the Al-SBA-15 molecular sieve, the amount of the medium strong acid is 0.6-1.0 mL/g, and preferably 0.7-0.9 mL/g.
Furthermore, in the Al-SBA-15 molecular sieve, the mass content of alumina is 2-85%, preferably 5-82%, and more preferably 5-75%. The amount of alumina in the molecular sieve can be adjusted within wide limits and can be, for example, 10%, 15%, 16%, 18%, 20%, 25%, 30%, 32%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 75%, etc.
Further, the pore distribution of the Al-SBA-15 molecular sieve also comprises: the pore volume of the pores with the pore diameter of 4-15 nm is 40-70%, preferably 45-65%, and more preferably 50-60% of the total pore volume.
Further, the properties of the Al-SBA-15 molecular sieve are as follows: the specific surface area is 550 to 850m2Preferably 650 to 750 m/g2The total pore volume is 0.7 to 1.3mL/g, preferably 0.9 to 1.2 mL/g.
The second aspect of the present invention provides a method for preparing a hydrorefining catalyst, comprising:
(I) preparing an Al-SBA-15 molecular sieve by using amorphous silica-alumina dry gel as a raw material and a P123 triblock copolymer as a template agent;
(II) mixing the Al-SBA-15 mesoporous molecular sieve prepared in the step (I), alumina and water to prepare slurry;
(III) adding a solution containing an active metal component and a dispersion liquid containing nano magnesium oxide into the slurry prepared in the step (II) to obtain mixed slurry;
(IV) filtering, washing and carrying out heat treatment on the mixed slurry prepared in the step (III) to obtain a first catalyst precursor;
(V) crushing, kneading, molding, drying and roasting the first catalyst precursor prepared in the step (IV) to obtain a second catalyst precursor;
(VI) dipping the second catalyst precursor prepared in the step (V) by using an aqueous solution containing an organic auxiliary agent, and carrying out heat treatment on the dipped sample to obtain the final hydrofining catalyst.
Further, step (I) is a method for preparing the Al-SBA-15 molecular sieve, which comprises the following steps:
(1) mixing amorphous silica-alumina dry gel and water to form slurry;
(2) preparing an acidic solution containing a P123 triblock copolymer;
(3) mixing the slurry prepared in the step (1) with the acidic solution containing the P123 triblock copolymer prepared in the step (2); and crystallizing to obtain the Al-SBA-15 molecular sieve.
Further, the mass content of the alumina in the amorphous silica-alumina dry gel is 2-85%, preferably 5-82%, and more preferably 5-75%. The mass content of the aluminum oxide can be adjusted within wide ranges, and can be, for example, 10%, 15%, 16%, 18%, 20%, 25%, 30%, 32%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 75%, and the like.
Further, the properties of the amorphous silica-alumina dry gel are as follows: the specific surface area is 400-650 m2Per g, preferably 450 to 600m2The pore volume is 0.52-1.8 mL/g, preferably 0.85-1.5 mL/g, and the pore distribution is as follows: the pore volume with the pore diameter of 4-15 nm accounts for 85% -95% of the total pore volume, and the pore volume with the pore diameter of more than 15nm accounts for less than 5% of the total pore volume.
Further, the amorphous silica-alumina dry gel in the step (1) is prepared by a carbonization method, and can be prepared by the following steps:
a. respectively preparing a sodium aluminate solution and a sodium silicate solution;
b. adding part or all of sodium silicate solution into sodium aluminate solution, and introducing CO2Controlling the reaction temperature of the gas to be 10-40 ℃, preferably 15-35 ℃, and controlling the pH value of the gel to be 8-11; wherein when CO is introduced2When the gas amount accounts for 40-100 percent of the total input amount, preferably 50-80 percent, adding the rest sodium silicate solution;
c. c, ventilating and stabilizing the mixture for 10-30 minutes under the temperature and pH value control of the step b;
d. c, filtering the solid-liquid mixture obtained in the step c, and washing a filter cake;
e. d, pulping the filter cake obtained in the step d, then carrying out hydro-thermal treatment, filtering and drying to obtain the amorphous silica-alumina dry gel; the hydrothermal treatment conditions were as follows: treating for 2-10 hours at 120-150 ℃ and under the water vapor pressure of 0.5-4.0 MPa.
Further, in the step a, the concentration of the sodium aluminate solution is 15-55 gAl2O3A further optional amount of 15 to 35gAl2O3L, the concentration of the sodium silicate solution is 50-200 gSiO2A further amount of 50 to 150g SiO2/L。
Further, in the step b, part or all of the sodium silicate solution is added, namely 5wt% -100 wt% of the total added sodium silicate solution. Said CO2The concentration of the gas is 30-60 v%. And c, ventilating and stirring in the gelling process in the step b.
Further, the specific process of step b is as follows: (1) adding all sodium silicate into sodium aluminate, and introducing CO2A gas; (2) adding part of sodium silicate into sodium aluminate, and introducing all CO2Gas, then adding the remaining sodium silicate solution to the mixture; (3) after adding part of sodium silicate to sodium aluminate, part of CO is introduced2Gas, then CO is introduced2The gas was added to the remaining sodium silicate solution.
Further, filtering the slurry obtained in the step d, washing the slurry with deionized water at the temperature of 50-95 ℃ until the slurry is nearly neutral,
and further, mixing the filter cake obtained in the step e according to a solid-liquid volume ratio of 8: 1-12: 1, adding water and pulping.
Further, the drying in the step e can be performed by a conventional method, and can be performed for 6-8 hours at 110-130 ℃.
Further, the mass ratio of the amorphous silica-alumina dry gel to water in the step (1) is 10: 90-30: 70, preferably 15: 85-25: 75.
further, the pH value of the acidic solution in the step (2) is 1-5, preferably 1.2-2.3, and the mass content of the P123 triblock copolymer in the acidic solution is 0.5-5.0%, preferably 0.8-2.8%.
Further, in step (2), the P123 triblock copolymer is added to a dilute acid (such as dilute hydrochloric acid) at a concentration of H+0.05 to 0.3mol/L, preferably 0.1 to 0.2 mol/L, and more preferably 0.13 to 0.18 mol/L; in order to sufficiently dissolve the P123 triblock copolymer, the temperature system is controlled to 10 to 60 ℃, preferably 20 to 40 ℃, and more preferably 25 to 35 ℃.
Further, in the step (3), the slurry prepared in the step (1) is mixed with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), and the amounts of the slurry prepared in the step (1) and the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2) are such that the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 0.5:1 to 5:1, preferably 1:1 to 5:1, and more preferably 1:1 to 3: 1.
Further, the crystallization temperature in the step (3) is 80-120 ℃, and preferably 90-110 ℃; the crystallization time is 10-35 h, preferably 16-24 h; the pH value in the crystallization process is controlled to be 2.0-5.0, preferably 3.2-4.8.
Further, after the crystallization step in step (3), the Al-SBA-15 molecular sieve may be separated from the obtained mixture by any conventionally known means, for example, by at least one of filtration, washing and drying. The filtration can adopt suction filtration. The washing can be performed by using deionized water as a washing solution. The drying can be carried out at 80-150 ℃, preferably 90-130 ℃, and the drying time is 2-12 hours, preferably 3-6 hours. The drying may be carried out at atmospheric pressure.
Further, the molecular sieve prepared by the above method may be calcined to remove the template agent and moisture, etc., if necessary. The roasting can be carried out according to any mode conventionally known in the art, for example, the roasting temperature is generally 450-600 ℃, preferably 480-580 ℃, further preferably 500-560 ℃, and the roasting time is 2-10 hours, preferably 3-6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
Further, the properties of the alumina in step (II) are as follows: the specific surface area is 150-450 m2Preferably 230 to 340 m/g2(ii)/g; the pore volume is 0.4-1.4 mL/g, preferably 0.8-1.2 mL/g, and the average pore diameter is 8-14 nm.
Further, in the step (II), the mass concentration of the nano magnesium dioxide in the dispersion liquid containing the nano magnesium oxide is 20-50%. The dispersion liquid containing the nano magnesium dioxide can adopt a commercially available nano magnesium dioxide dispersion liquid, and the particle size of the nano magnesium oxide is 20-40 nm.
Further, adding the two solutions prepared in the step (III) into the slurry prepared in the step (II) simultaneously or respectively;
further, stirring the mixed slurry prepared in the step (III) under the action of ultrasonic waves, wherein the power of the ultrasonic waves is 5-100 Hz, and preferably 20-60 Hz; the temperature is controlled to be 20-80 ℃, preferably 40-60 ℃, and the stirring time is 10-80 min, preferably 20-60 min.
Further, in the step (IV), the filtering and washing are carried out by adopting conventional means in the field, the temperature of the heat treatment is 60-180 ℃, the time is 0.5-20 hours, preferably 60-120 ℃, and the time is 1-8 hours, and the heat treatment is carried out under the protection of nitrogen or inert gas.
Further, in the step (V), the kneading and extruding strip is performed by a conventional method in the art, and conventional aids, such as peptizing acid, extrusion aid, binder, etc., may be added during the kneading or forming process, and the peptizing acid may be at least one of citric acid and nitric acid, preferably citric acid and nitric acid. The binder may be a small pore alumina. The extrusion aid can be sesbania powder and the like.
Further, in the step (V), the drying conditions are: the drying temperature is 60-220 ℃, preferably 90-180 ℃, and the drying time is 0.5-10 h, preferably 1-5 h. The roasting conditions are as follows: the roasting conditions were as follows: the roasting temperature is 350-500 ℃, preferably 400-480 ℃, and the roasting time is 0.5-10 h, preferably 1-5 h.
Further, the organic auxiliary agent in step (VI) is one or a combination of more of ribitol, D-mannitol and stachyose.
Further, in the step (VI), the aqueous solution containing the organic auxiliary may be prepared by sufficiently dissolving the organic auxiliary in water.
Further, the heat treatment in the step (VI) is preferably two-step heat treatment, wherein the temperature of the first heat treatment is 80-120, preferably 90-110 ℃, the time is 0.5-5 hours, preferably 1-3 hours, the temperature of the second heat treatment is 120-200 ℃, preferably 150-180 ℃, the time is 0.5-5 hours, preferably 1-3 hours.
Furthermore, the hydrofining catalyst can also contain conventional additives, such as at least one of P, B, Ti, Zr and the like, wherein the content of the additives is less than 10% of the weight of the hydrofining catalyst by weight of the catalyst, and can be 0.1% -8.0%.
The invention also provides an application of the hydrofining catalyst.
Further, the application is that the hydrofining catalyst is applied to the hydrodenitrogenation reaction of shale oil.
Further, the reaction conditions of the hydrofining catalyst applied to the hydrodenitrogenation reaction of the shale oil are as follows: the total reaction pressure is 8-16 MPa, and the liquid hourly space velocity is 0.2-8.2 h-1The volume ratio of hydrogen to oil is 500: 1-1500: 1, the reaction temperature is 350-400 ℃.
The shale oil has the following properties: the shale oil has a nitrogen content of more than 1wt%, a sulfur content of more than 0.5wt% and an oxygen content of more than 0.8wt%, and compared with the conventional crude oil, the shale oil has high content of unsaturated aromatic hydrocarbon, impurities and metals.
Compared with the prior art, the hydrofining catalyst and the preparation method thereof have the following advantages:
(1) the Al-SBA-15 molecular sieve adopted by the hydrofining catalyst carrier can adjust the acid content of the Al-SBA-15 molecular sieve according to the characteristic requirements of raw materials. The addition of the molecular sieve can obviously improve the acid property of the catalyst, reduce the content of strong acid, obviously increase the content of medium strong acid and well improve the intrinsic activity of the catalyst; secondly, the Al-SBA-15 molecular sieve of the invention still shows the regularity of mesoporous structure even under the condition of very high aluminum content (for example, the mass percentage of alumina in the chemical composition of the molecular sieve is higher than 7 wt%), and the regularity can be characterized by the pore distribution of the molecular sieve (especially the pore volume ratio of pores with the diameter of less than 4 nm). As a corroboration, even if the mass percentage of the alumina in the chemical composition of the Al-SBA-15 molecular sieve is widely changed from 2% to 85%, the pore volume of the pores with the diameter of less than 4nm is still less than 20% of the total pore volume, and the integrity and the regularity of the mesoporous structure are maintained, which are not possessed by the Al-SBA-15 molecular sieve manufactured by the prior art. Therefore, after the Al-SBA-15 molecular sieve is added, the pore structure of the catalyst carrier can migrate towards the mesoporous direction, which is beneficial to the reaction of macromolecular polycyclic aromatic hydrocarbons in shale oil; the Al-SBA-15 mesoporous molecular sieve and the alumina in the carrier are mutually coordinated in use performance to generate better synergistic catalytic action, and the Al-SBA-15 mesoporous molecular sieve is added to obviously improve the concentration of active metal components on the surface of the carrier, namely the dispersion degree of the active metal components is increased, which is beneficial to generating more active sites and improving the reaction activity of the catalyst.
(2) The hydrofining catalyst also contains an organic auxiliary agent, so that the acid property of the catalyst can be further optimized, and the denitrification activity of the catalyst is obviously increased; meanwhile, the added organic auxiliary agent can weaken the acting force between the active component and the carrier, the active component is easy to reduce, a large number of hydroxyl groups on the surface of the organic auxiliary agent can be complexed with the active component, the effective active site of the catalyst is further increased, and the comprehensive use performance of the catalyst is improved.
(3) The hydrofining catalyst also contains nano magnesium oxide, so that the surface acidity of the catalyst can be optimized, the amount of strong acid is reduced, the amounts of medium strong acid and weak acid are proper, the water resistance of the catalyst is improved, and the strength of the catalyst is almost unchanged after long-time operation. Meanwhile, the denitrification activity of the catalyst is well improved, the running period of the device is prolonged, and the running cost is reduced.
Drawings
FIG. 1 is an XRD pattern of the Al-SBA-15 molecular sieve obtained in example 1 of the present invention.
Detailed Description
In the present invention, the Al-SBA-15 molecular sieve means that aluminum atoms are introduced into the SBA-15 molecular sieve, the existence state of the aluminum atoms in the SBA-15 molecular sieve is not particularly limited, and a part of the aluminum atoms are generally distributed on the framework of the SBA-15 molecular sieve.
In the invention, the determination of the L acid or the B acid adopts an infrared spectroscopy, an instrument adopts an American Nicot Fourier infrared spectrometer-6700, and the determination method comprises the following steps: weighing 20mg of sample with particle size less than 200 meshes, pressing into sheet with diameter of 20mm, placing on sample rack of absorption cell, placing 200mg sample into cup of instrument, connecting absorption cell and adsorption tube, vacuumizing until vacuum degree reaches 4 × 10-2And Pa, heating to 500 ℃, keeping for 1 hour to remove adsorbates on the surface of the sample, cooling to room temperature, adsorbing pyridine to saturation, continuously heating to 160 ℃, balancing for 1 hour, and desorbing the physically adsorbed pyridine to obtain the acid quantities of infrared total acid, B acid and L acid, wherein the acid quantity unit of the B acid and the L acid is mmol/L.
In the invention, NH is adopted as the medium strong acid3TPD method. The adopted instrument is an Auto-Chem II 2920 chemical adsorption instrument of Mike instruments. Adopting ammonia as an adsorption and desorption medium and helium as a carrier gas, and obtaining the acid quantities of different desorption temperature areas by adopting temperature programmed desorption and chromatographic analysis, wherein the ammonia desorption temperature corresponding to the acid quantity of weak acid is 250-400 ℃ corresponding to the acid quantity of strong acid in the temperature range of 150-250 ℃, the ammonia desorption temperature corresponding to the acid quantity of strong acid is 400-450 ℃, and the acid quantity unit is as follows: mL/g is the amount of ammonia adsorbed per gram of molecular sieve. The sum of weak, medium and strong acids is the total acid amount.
In the invention, the specific surface area, the pore volume and the pore distribution are measured by adopting an ASAP2405 physical adsorption instrument, and the measuring method comprises the following steps: after the sample is processed, liquid N2Used as adsorbate, the adsorption temperature is-196 ℃, and analysis and test are carried out. Wherein the specific surface area is calculated by a BET method, and the pore volume and the pore distribution are calculated by a BJH method.
In the present invention, the XPS-characterized metal dispersion is measured by a Multilab2000X photoelectron spectrometer, U.S.A. MgK alpha is used as an excitation source, the energy is 1253.6 eV, and the power is 200W. And C1s (284.6 eV) of a pollution carbon peak is taken as a calibration standard, and the influence of the charge effect is subtracted to determine the real binding energy of the sample.
In the present invention, XRD was measured using an X-ray diffractometer model D/max2500 manufactured by Japan science, under the following test conditions: the voltage is 40KV, the current is 80mA, a CuK alpha target is selected, and the incident wavelength is 0.15405 nm.
The effects and effects of the technical solution of the present invention are further illustrated by the following examples and comparative examples, but the present invention should not be construed as being limited to these specific examples, and the following examples and comparative examples of the present invention are given as percentages by mass unless otherwise specified.
Example 1
Preparation of Al-SBA-15 molecular sieve
(1) Preparation of amorphous silica-alumina dry gel A1 and slurry: sodium aluminate solution concentration 20gAl2O3Per L, sodium silicate solution concentration 60gSiO2Putting 0.75L of sodium aluminate solution into a gelling tank, adding 0.35L of sodium silicate solution, controlling the reaction temperature to be 20 ℃, and introducing 40 v% CO2Gas, introduction of CO2When the gas accounts for 50 percent of the total input amount, 0.20L of sodium silicate solution is added while introducing gas, the pH value of the formed gel is controlled to be 9.7, then the ventilation is stabilized for 20 minutes, the slurry is filtered and washed to be neutral by deionized water at 65 ℃, a filter cake is added with water according to the solid-liquid volume ratio of 12: 1 for pulping, the treatment is carried out for 2 hours at 120 ℃ under the water vapor pressure of 3.5MPa, and the amorphous silica-alumina product A1 is obtained by crushing and sieving after the drying is carried out for 6 hours at 120 ℃. Mixing the prepared amorphous silica-alumina A1 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 23: 77;
(2) preparing an acidic solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.13mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.3, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 25 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.6 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), crystallizing, filtering, drying and roasting to prepare an Al-SBA-15 molecular sieve, wherein the number is A-S-1, the mass ratio of the P123 triblock copolymer to amorphous silica-alumina in a mixed system is 1.2:1, the crystallization temperature is 90 ℃, and the crystallization time is 20 hours; the pH value is controlled to be 3.3 in the crystallization process, the drying temperature is controlled to be 100 ℃, the drying time is 3 hours, the roasting temperature is controlled to be 550 ℃, the roasting time is 3 hours, and the properties of the A-S-1 molecular sieve are shown in Table 1. The XRD pattern of the A-S-1 molecular sieve obtained in example 1 is shown in FIG. 1, which shows the characteristic peak of Al-SBA-15 molecular sieve.
(II) preparing a molybdenum-nickel-phosphorus heteropoly acid solution A, wherein the composition of the solution MoO3Weighing 10g of nano magnesium oxide dispersion liquid (a product produced by Hangzhou Wanjing new material company, wherein the content of magnesium oxide in the dispersion liquid is 30wt%, and the particle size is 30 nm), and diluting the nano magnesium oxide dispersion liquid to 100mL by using deionized water to obtain a solution B, wherein the content of NiO is 45.5g/100mL, the content of NiO is 7.5g/100mL, and the content of P is 3.5g/100 mL; weighing 8g of A-S-1 molecular sieve and 92g of alumina dry glue powder, putting the weighed materials into 6L of deionized water, stirring and dissolving the materials to uniformly disperse the two kinds of powder in a system to obtain slurry C, adding the solution A and the solution B into the slurry C in a concurrent flow manner, stirring under the condition of ultrasonic power of 52Hz at the temperature of 45 ℃, treating for 40min to obtain mixed slurry, filtering, washing, and then carrying out heat treatment for 4 hours at the temperature of 110 ℃ under the protection of nitrogen to obtain a first catalyst precursor containing nano magnesium oxide and active components; crushing the first precursor, adding 4g of sesbania powder, putting into a rolling machine, dissolving 4g of citric acid and 12.3g (the concentration is 65%) of nitric acid in 125mL of deionized water to prepare an acid solution, uniformly pouring into the rolling machine, rolling for 25min to obtain a paste, extruding the paste into 1.7mm clover on a strip extruding machine, drying for 4 hours at 130 ℃, and roasting for 3 hours at 450 ℃ to obtain a second catalyst precursor; and (3) impregnating the second catalyst precursor by using a water solution containing stachyose, wherein the molar ratio of the used amount of the stachyose to Mo atoms is 1:1,the impregnated sample is dried at room temperature, then is subjected to heat treatment at 120 ℃ for 3h and at 150 ℃ for 1h to obtain the final finished catalyst C-1, and the main physical properties are shown in tables 2 and 3.
Example 2
Preparation of Al-SBA-15 molecular sieve
(1) Preparation of amorphous silica-alumina dry gel A2: sodium aluminate solution concentration 30gAl2O3Per L, sodium silicate working solution concentration 90gSiO2L, putting 1.25L of sodium aluminate solution into a gel forming tank, then adding 0.65L of sodium silicate solution, controlling the reaction temperature to be 32 ℃, and introducing 52 v% CO2Stopping gas when the pH value reaches 9.9, then ventilating and stabilizing for 20 minutes, washing to be neutral, adding water into a filter cake according to the solid-liquid volume ratio of 9: 1 for pulping, treating for 3 hours at the temperature of 130 ℃ under the water vapor pressure of 3.9MPa, drying for 8 hours at the temperature of 130 ℃, crushing and sieving to obtain an amorphous silica-alumina product A2. Mixing the prepared amorphous silica-alumina A2 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 25: 75;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.16mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.0 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); crystallizing, filtering, drying and roasting to obtain an Al-SBA-15 molecular sieve, wherein the number is A-S-2, the mass ratio of a P123 triblock copolymer to amorphous silica-alumina in a mixed system is 2:1, the crystallization temperature is 93 ℃, and the crystallization time is 18 hours; the pH value is controlled to be 4.7 in the crystallization process, the drying temperature is controlled to be 120 ℃, the drying time is 4 hours, the roasting temperature is controlled to be 530 ℃, and the roasting time is 5 hours. The A-S-2 molecular sieve properties are shown in Table 1. The XRD pattern of the A-S-2 molecular sieve is similar to that of figure 1, and shows the characteristic peak of the Al-SBA-15 molecular sieve.
(II) preparing a molybdenum-nickel-phosphorus heteropoly acid solution A, wherein the composition of the solution MoO3Weighing 8g of nano magnesium oxide dispersion (same as example 1) with the content of 45.5g/100mL, the content of NiO of 7.5g/100mL and the content of P of 3.5g/100mL, and diluting the nano magnesium oxide dispersion to 100mL by using deionized water to obtain a solution B; weighing 6g of A-S-2 molecular sieve and 92g of alumina dry glue powder, putting the weighed materials into 6L of deionized water, stirring and dissolving the materials to uniformly disperse the two kinds of powder in a system to obtain slurry C, adding the solution A and the solution B into the slurry C in a parallel flow manner, stirring under the condition of ultrasonic power of 50Hz at the temperature of 48 ℃, treating for 40min to obtain mixed slurry, filtering, washing, and then carrying out heat treatment for 4 hours at the temperature of 110 ℃ under the protection of nitrogen to obtain a first catalyst precursor containing nano magnesium oxide and active components; crushing the first catalyst precursor, adding 4g of sesbania powder, putting into a rolling machine, dissolving 4g of citric acid and 11.9g (the concentration is 65%) of nitric acid in 132mL of deionized water to prepare an acid solution, uniformly pouring into the rolling machine, rolling for 25min to obtain a paste, extruding the paste into 1.7mm clovers on a strip extruding machine, drying at 120 ℃ for 4 hours, and roasting at 440 ℃ for 3 hours to obtain a second catalyst precursor; impregnating the second catalyst precursor with an aqueous solution containing a ribitol, wherein the ribitol is used in an amount such that the molar ratio of the ribitol to the Mo atom is 1.5: 1, after the impregnated sample is dried at room temperature, the heat treatment is carried out for 3h at 110 ℃ and 1h at 160 ℃ to obtain the final finished catalyst C-2, and the main physical properties are shown in tables 2 and 3.
Example 3
Preparation of Al-SBA-15 molecular sieve and slurry
(1) Preparation of amorphous silica-alumina dry gel A3: sodium aluminate solution concentration 30gAl2O3Per L, sodium silicate solution concentration 50gSiO2Putting 0.75L of sodium aluminate solution into a gelling tank, adding 0.12L of sodium silicate solution, controlling the reaction temperature at 23 ℃, and introducing 48 v% CO2Gas, introduction of CO2When gas accounts for 50% of total input amount, adding 0.20L sodium silicate solution while introducing gas, controlling pH value of gelatinized gel to 8.8, then ventilating and stabilizing for 20 min, filtering slurry, washing with 75 deg.C deionized water to neutrality, adding water into filter cake according to solid-liquid volume ratio of 11: 1, pulping, steaming at 120 deg.C and 3.5MPaTreating under steam pressure for 2 hr, drying at 120 deg.C for 6 hr, pulverizing, and sieving to obtain amorphous silica-alumina product A3. Mixing the prepared amorphous silica-alumina A3 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 24: 76;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.16mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.2 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); crystallizing, filtering, drying and roasting to obtain an Al-SBA-15 molecular sieve, wherein the number is A-S-3, the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 2.5:1, the crystallization temperature is 98 ℃, and the crystallization time is 20 hours; the pH value is controlled to be 4.3 in the crystallization process, the drying temperature is controlled to be 120 ℃, the drying time is 5 hours, the roasting temperature is controlled to be 540 ℃, and the roasting time is 5 hours. The A-S-3 molecular sieve properties are shown in Table 1. The XRD pattern of the A-S-3 molecular sieve is similar to that of figure 1, and shows the characteristic peak of the Al-SBA-15 molecular sieve.
(II) preparing a molybdenum-nickel-phosphorus heteropoly acid solution A, wherein the composition of the solution MoO3Weighing 12g of nano magnesium oxide dispersion (a product produced by Hangzhou Wanjing new material Co., Ltd., the content of magnesium oxide in the dispersion is 30wt%, the particle size is 35 nm), and diluting the nano magnesium oxide dispersion to 100mL by using deionized water to obtain a solution B, wherein the content of NiO is 45.5g/100mL, the content of NiO is 7.5g/100mL, and the content of P is 3.5g/100 mL; weighing 10g of A-S-3 molecular sieve and 92g of alumina dry glue powder, putting the weighed materials into 6L of deionized water, stirring and dissolving the materials to uniformly disperse the two kinds of powder in a system to obtain slurry C, adding the solution A and the solution B into the slurry C in a parallel flow manner, stirring under the condition of ultrasonic power of 55Hz, treating at the treatment temperature of 50 ℃ for 45min to obtain mixed slurry, filtering and washing, and then carrying out heat treatment at the temperature of 120 ℃ for 4 hours under the protection of nitrogen to obtain the sodium-containing powderA first catalyst precursor of magnesium oxide and active components; crushing the first catalyst precursor, adding 4g of sesbania powder, putting into a rolling machine, dissolving 4g of citric acid and 12.5g (the concentration is 65%) of nitric acid in 135mL of deionized water to prepare an acid solution, uniformly pouring into the rolling machine, rolling for 25min to obtain a paste, extruding the paste into 1.7mm clovers on a strip extruding machine, drying at 120 ℃ for 4 hours, and roasting at 450 ℃ for 3 hours to obtain a second catalyst precursor; impregnating the second catalyst precursor with an aqueous solution containing a ribitol, wherein the ribitol is used in an amount such that the molar ratio of the ribitol to the Mo atom is 2:1, after the impregnated sample is dried at room temperature, the heat treatment is carried out for 3h at 120 ℃ and 1.5h at 165 ℃ to obtain the final finished catalyst C-3, and the main physical properties are shown in tables 2 and 3.
Example 4
Preparation of Al-SBA-15 molecular sieve
The other conditions are the same as example 1, except that in the step (1) of preparing the amorphous silica-alumina dry gel A1 and the slurry, the pH value of the gel is controlled to be 9.8, an amorphous silica-alumina product A4 is obtained, and the finally prepared molecular sieve A-S-4 is obtained. The XRD pattern of the A-S-4 molecular sieve is similar to that of figure 1, and shows the characteristic peak of the Al-SBA-15 molecular sieve.
(II) preparing a molybdenum-nickel-phosphorus heteropoly acid solution A, wherein the composition of the solution MoO3Weighing 15g of nano magnesium oxide dispersion (same as example 1) with the content of 45.5g/100mL, the content of NiO of 7.5g/100mL and the content of P of 3.5g/100mL, and diluting the nano magnesium oxide dispersion to 100mL by using deionized water to obtain a solution B; weighing 12g of A-S-4 molecular sieve and 120g of alumina dry glue powder, putting the A-S-4 molecular sieve and 120g of alumina dry glue powder into 6L of deionized water, stirring and dissolving the two kinds of powder to uniformly disperse the two kinds of powder in a system to obtain slurry C, adding the solution A and the solution B into the slurry C in a concurrent flow manner, stirring under the condition of ultrasonic power of 55Hz, treating at the treatment temperature of 50 ℃ for 45min to obtain mixed slurry, filtering and washing, and then carrying out heat treatment at the temperature of 120 ℃ for 4 hours under the protection of nitrogen to obtain a first catalyst precursor containing nano magnesium oxide and active components; crushing the first catalyst precursor, adding 5g of sesbania powder, dissolving 4g of citric acid and 12.8g (the concentration is 65%) of nitric acid in 138mL of deionized water to prepare an acid solution, uniformly pouring the acid solution into a rolling machine, rolling for 25min to obtain a paste,extruding 1.7mm clover on a strip extruder, drying for 4 hours at 110 ℃, roasting for 3 hours at 450 ℃ to obtain a second catalyst precursor, and impregnating the second catalyst precursor with an aqueous solution containing D-mannitol, wherein the molar ratio of the D-mannitol to Mo atoms is 0.8: 1, after the impregnated sample is dried at room temperature, the heat treatment is carried out for 3h at 120 ℃ and 1.8h at 175 ℃ to obtain the final finished catalyst C-4, and the main physical properties are shown in tables 2 and 3.
Example 5
Preparation of Al-SBA-15 molecular sieve
(1) Preparation of amorphous silica-alumina dry gel A5 and slurry: sodium aluminate solution concentration 20gAl2O3Per L, sodium silicate solution concentration 50gSiO2Putting 0.75L of sodium aluminate solution into a gelling tank, adding 0.12L of sodium silicate solution, controlling the reaction temperature at 23 ℃, and introducing 45 v% CO2Controlling the pH value of the formed gel to be 8.8, stopping the forming, ventilating and stabilizing for 20 minutes, filtering the slurry, washing the slurry by deionized water at 75 ℃ until the slurry is neutral, adding water into a filter cake according to the solid-liquid volume ratio of 11: 1, pulping the filter cake, treating the filter cake for 2 hours at 120 ℃ under the water vapor pressure of 3.5MPa, drying the filter cake for 6 hours at 120 ℃, and crushing and sieving the filter cake to obtain an amorphous silica-alumina product A5. Mixing the prepared amorphous silica-alumina A5 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 24: 76;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.16mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.8 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); crystallizing, filtering, drying and roasting to obtain an Al-SBA-15 molecular sieve, wherein the number is A-S-5, the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 2.5:1, the crystallization temperature is 98 ℃, and the crystallization time is 20 hours; the pH value is controlled to be 4.3 in the crystallization process, the drying temperature is controlled to be 120 ℃, the drying time is 5 hours, the roasting temperature is controlled to be 540 ℃, and the roasting time is 5 hours. The A-S-5 molecular sieve properties are shown in Table 1. The XRD pattern of the A-S-5 molecular sieve is similar to that of figure 1, and shows the characteristic peak of the Al-SBA-15 molecular sieve.
(II) preparing a molybdenum-nickel-phosphorus heteropoly acid solution A, wherein the composition of the solution MoO3Weighing 8g of nano magnesium oxide dispersion (same as example 1) with the content of 45.5g/100mL, the content of NiO of 7.5g/100mL and the content of P of 3.5g/100mL, and diluting the nano magnesium oxide dispersion to 100mL by using deionized water to obtain a solution B; weighing 15g of A-S-2 molecular sieve and 125g of alumina dry glue powder, putting the weighed materials into 8L of deionized water, stirring and dissolving the materials to uniformly disperse the two kinds of powder in a system to obtain slurry C, adding the solution A and the solution B into the slurry C in a concurrent flow manner, stirring under the condition of ultrasonic power of 53Hz, treating at 42 ℃ for 40min to obtain mixed slurry, filtering and washing, and then carrying out heat treatment at 120 ℃ for 4 hours under the protection of nitrogen to obtain a first catalyst precursor containing nano magnesium oxide and active components; crushing the first catalyst precursor, adding 5g of sesbania powder, putting into a rolling machine, dissolving 5g of citric acid and 13.5g (with the concentration of 65%) of nitric acid in 141mL of deionized water to prepare an acid solution, uniformly pouring into the rolling machine, rolling for 25min to obtain a paste, extruding the paste on a strip extruder to obtain 1.7mm clovers, drying at 120 ℃ for 4 hours, roasting at 430 ℃ for 3 hours to obtain a second catalyst precursor, and impregnating the second catalyst precursor with an aqueous solution containing D-mannitol and stachyose, wherein the molar ratio of the D-mannitol to Mo atom is 0.5:1, the molar ratio of the used stachyose to Mo atoms is 0.8: 1, after the impregnated sample is dried at room temperature, the heat treatment is carried out for 3h at 130 ℃ and 1.5h at 155 ℃ to obtain the final finished catalyst C-5, and the main physical properties are shown in tables 2 and 3.
Comparative example 1
(1) Preparation of shale oil hydrotreating catalyst carrier
Taking 120g of macroporous aluminum hydroxide dry rubber powder and 50g of small-pore alumina dry rubber powder, adding 5g of citric acid and sesbania powder respectively, and uniformly mixing. Then 155g of dilute aqueous nitric acid solution is uniformly added, wherein the mass of the nitric acid is 12.5g (the concentration is 65%). Kneading the materials for 25min, rolling for 25min, and extruding with 1.7mm diameter clover orifice plate. Drying at 120 deg.C for 4 hr, and calcining at 550 deg.C for 4 hr. The calcined support was designated Z-1.
(2) Catalyst preparation
Soaking the carrier Z-1 in soaking liquid containing Mo, Ni and P in the same volume, airing at room temperature, drying at 110 ℃ for 4h, and roasting at 435 ℃ for 3h to obtain the catalyst C-6. The catalyst properties are shown in tables 2 and 3.
Comparative example 2
Respectively weighing template agent triblock copolymer P123 and silicon source tetraethoxysilane, wherein the mass of the template agent P123 is 5.5g, and the mass of tetraethoxysilane is 10.2 g; adding a template agent and a silicon source into an HCl solution with the pH value of 2.8, and fully stirring for 30 hours at the temperature of 28 ℃; standing and crystallizing the stirred mixture for 20h at 120 ℃, washing with deionized water, and drying to obtain SBA-15. Pulping the obtained SBA-15 molecular sieve with a solid-to-liquid ratio of 1:10, adding the obtained SBA-15 molecular sieve into hydrochloric acid solution containing 23g of aluminum isopropoxide, heating to 100 ℃, stirring for 20 hours, filtering, washing, drying at 60 ℃ overnight, and roasting at 550 ℃ for 5 hours to obtain a mesoporous material A-S-8, wherein the properties are shown in Table 1.
The preparation method of the catalyst is the same as that of example 1, except that A-S-1 is changed to A-S-8, and the catalyst is numbered C-7. The catalyst properties are shown in tables 2 and 3.
Comparative example 3
6.2g of P123 was added to 600mL0.18mol/L hydrochloric acid solution, and after heating to 26 ℃ and stirring at a constant temperature for 6 hours, the solution was transparent after P123 was completely dissolved. Adding 5.2gY molecular sieve slurry, controlling pH at 3.3, stirring at constant temperature for reaction for 6 hr, and heating to 98 deg.C for hydrothermal crystallization for 24 hr. Then, the mixture is filtered, washed, dried at 120 ℃ for 6 hours and roasted at 550 ℃ for 6 hours to obtain Al-SBA-15 mesoporous molecular sieve, the serial number of which is A-S-9, and the properties of which are shown in Table 1.
The preparation method of the catalyst is the same as that of example 1, except that A-S-1 is changed to A-S-9, and the catalyst is numbered C-8. The catalyst properties are shown in tables 2 and 3.
Comparative example 4
Roasting and activating kaolin at 700 ℃ for 4h, weighing 12g of roasted kaolin, soaking for 4h by adopting 6mol/L hydrochloric acid, then carrying out suction filtration and washing by using deionized water until the kaolin is neutral, and drying; roasting the dried sample at 900 ℃ for 2 h; then the mixture is put into NaOH aqueous alkali of 5mol/L to react for 3h under high temperature and high pressure (the temperature is 160 ℃, the pressure is 0.5MPa), and after the reaction is finished, the pH value is adjusted to be 14.0. Then, the mesoporous material is dropwise added into a mixed solution of a surfactant and an acid (n (FSO-100)/n (P123) ═ 5.5), the concentration of hydrochloric acid is 7.5mol/L, the mixture is stirred and reacted for 24 hours at 40 ℃, the mixture is subjected to hydrothermal reaction for 48 hours at 160 ℃, and after filtration, washing and drying, the mesoporous material is roasted for 6 hours at 550 ℃ in a muffle furnace to obtain the mesoporous material A-S-10, wherein the properties of the mesoporous material are shown in Table 1.
The preparation method of the catalyst is the same as that of example 1, except that A-S-1 is changed to A-S-10, and the catalyst is numbered C-9. The catalyst properties are shown in tables 2 and 3.
Comparative example 5
Adding 4g of P123 into 2mol/L125mL hydrochloric acid solution, and stirring at 40 ℃ until the P123 is completely dissolved; adding 8.5g of tetraethoxysilane into hydrochloric acid solution containing P123, stirring for 4 hours, adding aluminum nitrate to enable the molar ratio of silicon to aluminum to be 35, continuing to stir for 20 hours, adding the solution into a 250mL reaction kettle, stirring for 48 hours at 100 ℃, cooling to room temperature, adjusting the pH value to 7.5 by using an ammonia water solution, continuously stirring, heating to 100 ℃, stirring for 72 hours, filtering, washing, drying overnight at 60 ℃, roasting for 6 hours at 550 ℃, and obtaining the mesoporous material A-S-11, wherein the properties are shown in Table 1.
The preparation method of the catalyst is the same as that of example 1, except that A-S-1 is changed to A-S-11, and the catalyst is numbered C-10. The catalyst properties are shown in tables 2 and 3.
TABLE 1 Al-SBA-15 molecular Sieve Properties
Item A-S-1 A-S-2 A-S-3 A-S-4 A-S-5
Specific surface area, m2/g 735 737 745 750 748
Alumina content, wt% 31.25 39.06 58.44 31.25 71.40
Pore volume, mL/g 1.17 1.13 1.09 1.15 1.13
Acid amount of medium strong acid, mL/g 0.76 0.77 0.82 0.85 0.83
B/L 0.317 0.261 0.245 0.321 0.332
Hole distribution,%
＜4nm 11.15 13.63 12.83 14.25 14.89
4～15nm 54.62 53.65 53.02 55.56 58.35
＞15nm 34.23 32.72 34.15 30.19 26.76
TABLE 1
Item A-S-8 A-S-9 A-S-10 A-S-11
Specific surface area, m2/g 706 720 695 708
Alumina content, wt% 17.25 4 8 13
Pore volume, mL/g 1.04 0.85 0.78 1.05
Acid amount of medium strong acid, mL/g 0.45 0.53 0.41 0.43
B/L 1.25 1.21 1.24 1.32
Hole distribution,%
＜4nm 43.05 42.69 46.28 45.36
4～15nm 37.56 38.25 35.69 36.45
＞15nm 19.39 19.06 18.03 18.19
TABLE 2 composition and Properties of the catalysts
Catalyst numbering C-1 C-2 C-3 C-4 C-5
Composition of
MoO3，wt% 23.30 23.80 23.50 23.6 23.8
NiO，wt% 4.2 3.9 3.8 4.6 4.2
P，wt% 1.6 1.7 1.8 1.6 1.3
Nanometer magnesia, wt% 2.4 3 3.6 4.5 5.4
Al-SBA-15 molecular sieve, wt.% 6.2 4.7 7.6 8.6 9.4
Properties of
Specific surface area, m2/g 223 225 228 226 228
Pore volume, mL/g 0.36 0.37 0.38 0.35 0.34
Acid distribution
Weak acid content% 31.37 35.75 37.58 34.58 33.65
Middle strong acid content% 58.62 55.23 54.30 56.89 57.26
Strong acid content% 10.01 9.02 8.12 8.53 9.09
Degree of dispersion
Mo/Al 0.172 0.178 0.180 0.176 0.178
Ni/Al 0.07 0.08 0.07 0.08 0.07
TABLE 2
Catalyst numbering C-6 C-7 C-8 C-9 C-10
Composition of
MoO3，wt% 23.91 23.30 23.30 23.30 23.30
NiO，wt% 3.93 4.2 4.2 4.2 4.2
P，wt% 1.49 1.6 1.6 1.6 1.6
Properties of
Specific surface area, m2/g 186 212 215 209 218
Pore volume, mL/g 0.30 0.31 0.32 0.33 0.33
Acid distribution
Weak acid content% 33.12 37.44 37.62 36.57 35.62
Middle strong acid content% 38.20 48.36 46.02 47.38 48.03
Strong acid content% 28.68 14.20 16.36 16.05 16.35
Degree of dispersion
Mo/Al 0.125 0.153 0.147 0.151 0.148
Ni/Al 0.05 0.04 0.05 0.07 0.06
TABLE 3 2000 hour run catalyst Strength comparison
Catalyst numbering C-1 C-2 C-3 C-4 C-5 C-6
Crushing strength of the new agent, N cm-1 162 163 165 162 163 165
Crush strength of catalyst after operation, N.cm-1 162 162 165 162 164 121
Catalyst evaluation
The catalyst activity evaluation experiments of the examples and comparative examples were carried out on a 100mL small fixed bed hydrogenation unit, and the catalysts were presulfided before the evaluation. The evaluation conditions of the catalyst are that the total reaction pressure is 14.5MPa, and the liquid hourly space velocity is 0.2h-1Hydrogen-oil volume ratio 1200: 1, the reaction temperature is 383 ℃. Properties of the raw oil for the activity evaluation test are shown in Table 4, and the results of the activity evaluation are shown in Table 5.
TABLE 4 Properties of the feed oils
Raw oil name Shale oil whole fraction
Density (20 ℃ C.)/g-cm-3 0.920
Distillation range/. degree.C
IBP/10% 167/248
30%/50% 316/374
70%/90% 428/501
95%/EBP -/663
Viscosity (50 ℃ C.)/mm2·s-1 3.471
Viscosity (100 ℃ C.)/mm2·s-1 11.70
Freezing point/. degree.C 35
Flash point/DEG C (closed)
Carbon residue in wt% 2.47
Acid value/(mgKOH). g-1 0.48
Asphaltenes, wt.% 0.08
S，wt% 0.53
N，wt% 1.09
C，wt% 84.17
H，wt% 11.35
O，wt% 0.85
Composition of mass spectrum, wt%
Paraffin hydrocarbon 19.3
Total cycloalkanes 27.1
Total aromatic hydrocarbons 32.7
Total gum 20.9
TABLE 5 Activity evaluation results
Catalyst numbering Nitrogen content, μ g-1
C-1 10.3
C-2 9.9
C-3 9.8
C-4 10.2
C-5 9.7
C-6 43.5
C-7 22.3
C-8 25.3
C-9 23.5
C-10 21.5
As can be seen from Table 5, compared with the comparative catalyst, the shale oil hydrotreating catalyst prepared by the invention has significantly improved hydrodenitrogenation activity and enhanced water resistance.
TABLE 6 Properties of amorphous silica-alumina
Amorphous silica-alumina numbering A1 A2 A3 A4 A5
Specific surface area, m2/g 512 537 528 535 519
Pore volume, mL/g 1.18 1.23 1.20 1.26 1.19
Hole distribution,%
4～15nm 88 86 87 92 93
＞15nm 3 4 3 3 2

Claims (16)

1. A hydrorefining catalyst characterized by: the hydrofining catalyst comprises: the catalyst comprises a carrier, an active metal component, nano magnesium oxide and an organic auxiliary agent, wherein the carrier comprises an Al-SBA-15 molecular sieve and aluminum oxide.
2. A hydrofinishing catalyst according to claim 1, wherein: the hydrofining catalyst has the following properties: the specific surface area is 180-240 m2The pore volume is 0.28-0.45 mL/g, and the content of the medium-strong acid accounts for 50-70% of the total acid content, preferably 53-63%.
3. A hydrofinishing catalyst according to claim 1, wherein: the organic auxiliary agent is one or a combination of more of ribitol, D-mannitol and stachyose.
4. A hydrofinishing catalyst according to claim 1, wherein: the active metal component is a metal in a VIII group and a metal in a VIB group, the metal in the VIII group is preferably Co and/or Ni, and the metal in the VIB group is preferably W and/or Mo; based on the weight of the hydrofining catalyst, the content of the VIII family metal calculated by oxide is 1wt% -15 wt%, preferably 3wt% -10 wt%, and the content of the VIB family metal calculated by oxide is 10wt% -30 wt%, preferably 15wt% -25 wt%.
5. A hydrorefining catalyst according to claim 4, characterized in that: in the hydrofining catalyst, by weight of the catalyst, the content of a carrier is 60% -74%, the content of an active metal component is 11% -31% by weight of an oxide, and the content of nano magnesium oxide is 1% -6%; in the hydrofining catalyst, the mole ratio of the content of the organic auxiliary agent to the VIB group metal atom is 0.01: 1-12: 1, preferably 0.01: 1-10: 1.
6. a hydrofinishing catalyst according to claim 1, wherein: in the carrier, the weight content of the Al-SBA-15 molecular sieve is 2-20%, preferably 3-12%, and the weight content of the alumina is 80-98%, preferably 88-97%.
7. A hydrofinishing catalyst according to claim 1, wherein: the pore distribution of the Al-SBA-15 molecular sieve comprises the following components: the pore volume occupied by pores with a pore diameter <4nm is less than 20%, preferably less than 15% of the total pore volume; in the Al-SBA-15 molecular sieve, the ratio of B acid to L acid is below 1; the amount of the medium strong acid is 0.6 to 1.0mL/g, preferably 0.7 to 0.9 mL/g.
8. A hydrofinishing catalyst according to claim 1, wherein: in the Al-SBA-15 molecular sieve, the mass content of alumina is 2-85%, preferably 5-82%, and more preferably 5-75%.
9. The process for producing a hydrorefining catalyst according to any of claims 1 to 8, comprising:
(I) preparing an Al-SBA-15 molecular sieve by using amorphous silica-alumina dry gel as a raw material and a P123 triblock copolymer as a template agent;
(II) mixing the Al-SBA-15 mesoporous molecular sieve prepared in the step (I), alumina and water to prepare slurry;
(III) adding a solution containing an active metal component and a dispersion liquid containing nano magnesium oxide into the slurry prepared in the step (II) to obtain mixed slurry;
(IV) filtering, washing and carrying out heat treatment on the mixed slurry prepared in the step (III) to obtain a first catalyst precursor;
(V) crushing, kneading, molding, drying and roasting the first catalyst precursor prepared in the step (IV) to obtain a second catalyst precursor;
(VI) dipping the second catalyst precursor prepared in the step (V) by using an aqueous solution containing an organic auxiliary agent, and carrying out heat treatment on the dipped sample to obtain the hydrofining catalyst.
10. The method of claim 9, wherein: the method for preparing the Al-SBA-15 molecular sieve in the step (I) comprises the following steps:
(1) mixing amorphous silica-alumina dry gel and water to form slurry;
(2) preparing an acidic solution containing a P123 triblock copolymer;
(3) mixing the slurry prepared in the step (1) with the acidic solution containing the P123 triblock copolymer prepared in the step (2); and crystallizing to obtain the Al-SBA-15 molecular sieve.
11. The method of claim 9, wherein: in the step (II), the mass concentration of the nano magnesium dioxide in the dispersion liquid containing the nano magnesium oxide is 20-50%; the particle size of the nano magnesium oxide is 20 nm-40 nm.
12. The method of claim 9, wherein: the properties of the alumina in step (II) are as follows: the specific surface area is 150-450 m2Preferably 230 to 340 m/g2(ii)/g; the pore volume is 0.4-1.4 mL/g, preferably 0.8-1.2 mL/g, and the average pore diameter is 8-14 nm.
13. The method of claim 9, wherein: stirring the mixed slurry prepared in the step (III) under the action of ultrasonic waves, wherein the power of the ultrasonic waves is 5-100 Hz, and preferably 20-60 Hz; the temperature is controlled to be 20-80 ℃, preferably 40-60 ℃, and the stirring time is 10-80 min, preferably 20-60 min.
14. The method of claim 9, wherein: the heat treatment in the step (VI) is two-step heat treatment, wherein the temperature of the first-step heat treatment is 80-120 ℃, preferably 90-110 ℃, and the time is 0.5-5 hours, preferably 1-3 hours, and the temperature of the second-step heat treatment is 120-200 ℃, preferably 150-180 ℃, and the time is 0.5-5 hours, preferably 1-3 hours.
15. An application of a hydrofining catalyst in a shale oil hydrodenitrogenation reaction is characterized in that: the catalyst is a hydrofinishing catalyst as claimed in any one of claims 1 to 8 or as prepared by the process of any one of claims 9 to 14.
16. Use according to claim 15, characterized in that: the shale oil has the following properties: nitrogen content > 1wt%, sulphur content > 0.5wt%, oxygen content > 0.8 wt%.
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