CN114453005B - Hydrofining catalyst and preparation method and application thereof - Google Patents

Hydrofining catalyst and preparation method and application thereof Download PDF

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CN114453005B
CN114453005B CN202011134765.6A CN202011134765A CN114453005B CN 114453005 B CN114453005 B CN 114453005B CN 202011134765 A CN202011134765 A CN 202011134765A CN 114453005 B CN114453005 B CN 114453005B
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catalyst
molecular sieve
content
sba
prepared
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CN114453005A (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
    • 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
    • B01J35/30—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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a hydrofining catalyst and a preparation method and application thereof. The hydrofining catalyst of the present invention 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 alumina. The hydrofining catalyst can deeply remove the nitrogen-containing compounds in shale oil, has good hydrogenation performance, meets the quality requirements of subsequent process production, and ensures the full play of the service performance of the cracking catalyst.

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 shale oil distillate oil hydrotreating process.
Background
In natural resources, oil shale and petroleum are mainly produced by the decomposition and coal formation of lower plankton such as algae. The shale oil "squeezed" from the oil shale is called "artificial petroleum" by low dry distillation, etc., and can be further processed and refined to prepare liquid fuels such as gasoline, kerosene, diesel oil, etc. The production process pollutes the environment in the early stage of exploitation of the oil shale due to the fact that the technology is not closed, and the development of the industry is limited. In recent years, with the progress of technology, this problem has been well solved. It is anticipated that shale oil will play an increasingly important role in the energy family in the current situation of shortage of petroleum resources and rising oil prices. 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 from being directly used as transportation fuel oil, so that NOx and SOx generated by a large amount of sulfur and nitrogen impurities have adverse effects on the environment.
The shale oil processing means mainly comprise two methods of non-hydrotreatment and hydrotreatment. Non-hydrotreatment generally includes acid-base refining, solvent refining, adsorption refining, addition of stabilizers, and the like. In the aspect of the hydrotreating method, the American oil refining company mainly carries out hydrotreating pretreatment on shale oil to remove sulfur, nitrogen, arsenic and other impurities in the shale oil, and then produces various oil products in a refinery according to the conventional processing technology; the Brazilian oil refining company divides shale oil into light fraction and heavy fraction, 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 oxides of the VIII and VIB groups in the periodic table into refractory inorganic porous materials, and generally adopts alumina, silica, titania, silicon carbide, boron oxide, zirconia and composite carriers combined together, prepare a catalyst precursor through an impregnation process, and prepare a finished catalyst through a plurality of steps of drying and roasting processes. The finished catalyst is presulfided before use, namely, the oxidation state catalyst is converted into the sulfidation state catalyst in the presence of hydrogen sulfide, sulfur-containing organic compounds or elemental sulfur, and hydrogenation reaction is carried out.
USP4419218 discloses a method for producing aviation kerosene by hydrocracking demetallized shale oil, wherein a hydrofinishing agent takes Mo-Ni-P as an active metal component, alumina as a carrier, a hydrocracking catalyst takes Co-Cr-Mo trimetallic as an active component, and a ZSM-12 molecular sieve as a carrier, the aviation kerosene yield reaches 70%, but the refining agent has poor effect, and further the quality of cracked products is affected.
CN1785512a discloses a process for preparing hydrocarbon cracking catalyst containing ferrous iron, the catalyst is composed of 5-20% of aluminium hydrogen phosphate, 5-15% of ferrous iron, and the balance of clay, and is suitable for hydrocarbon catalytic cracking reaction of fixed bed high nitrogen shale oil and high wax content crude oil in fixed bed, and has good cracking performance.
CN101590416a discloses a method for preparing a molybdenum-nickel hydrogenation catalyst, which comprises the steps of kneading and impregnating to prepare the catalyst, firstly adding molybdenum oxide, titanium-containing compound and phosphorus-containing compound into alumina and/or alumina precursor, then adding nitric acid solution, kneading, extruding to form strips, drying and roasting to obtain titanium-, phosphorus-and molybdenum-containing alumina formed products, impregnating with nickel-containing phosphoric acid solution, drying and roasting to obtain the molybdenum-nickel hydrogenation catalyst, wherein the catalyst has poor refining effect on distillate oil with high nitrogen content.
CN1052501a discloses a hydrofining catalyst and its preparation method, the catalyst uses silicon oxide-alumina as carrier, adopts three active metal components of W-Mo-Ni and boron auxiliary agent, adopts sectional impregnation method to make impregnation, and makes drying and roasting so as to obtain the invented finished product catalyst, when the nitrogen content is increased, the denitrification effect is not obvious.
The hydrotreating catalyst prepared by the prior art has low denitrification activity, particularly has poor denitrification effect when meeting shale oil distillate oil with high nitrogen content, and can directly influence the reaction performance of the catalyst in a subsequent cracking section reactor, thereby influencing the quality of cracked products, shortening the running period of the 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 treating shale oil, and a preparation method and application thereof. The hydrofining catalyst disclosed by the invention can deeply remove the nitrogen-containing compounds in shale oil, has good hydrogenation performance, meets the quality requirements of subsequent process production, and ensures the full play of the service performance of the cracking catalyst.
The first aspect of 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 alumina.
Further, the hydrofining catalyst has the following properties: the specific surface area is 180-240 m 2 Per g, 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%.
The active metal component is a group VIII metal and a group VIB metal, wherein the group VIII metal is preferably Co and/or Ni, and the group VIB metal is preferably W and/or Mo. The content of the group VIII metal in terms of oxide is 1-15 wt%, preferably 3-10 wt%, and the content of the group VI B metal in terms of oxide is 10-30 wt%, preferably 15-25 wt%, based on the weight of the final hydrofining catalyst.
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 oxide, and the content of the nano magnesium oxide is 1% -6%.
Further, in the hydrofining catalyst, the molar ratio of the content of the organic auxiliary agent to the atom of the group VIB metal is 0.01:1 to 12:1, preferably 0.01:1 to 10:1.
further, the organic auxiliary agent is one or a combination of a plurality of ribitol, D-mannitol and stachyose.
Further, 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 the pores with the pore diameter of <4nm is less than 20 percent, preferably less than 15 percent of the total pore volume; in the Al-SBA-15 molecular sieve, the ratio of B acid to L acid is below 1.
Further, the ratio of the B acid to the L acid in the Al-SBA-15 molecular sieve may be less than 0.8, less than 0.5 or less than 0.4. The ratio of the B acid to the L acid in the molecular sieve can be more than 0.1 or more than 0.2.
Further, in the Al-SBA-15 molecular sieve, the amount of the medium strong acid is 0.6-1.0 mL/g, preferably 0.7-0.9 mL/g.
Further, in the Al-SBA-15 molecular sieve, the mass content of the alumina is 2% -85%, preferably 5% -82%, and more preferably 5% -75%. The content of alumina in the molecular sieve may be adjusted within a wide range, 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 further 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 Al-SBA-15 molecular sieve has the following properties: specific surface area of 550-850 m 2 Preferably 650-750 m per gram 2 Per gram, the total pore volume is 0.7-1.3 mL/g, preferably 0.9-1.2 mL/g.
The second aspect of the present invention provides a method for producing a hydrofining catalyst, comprising:
(I) Preparing an Al-SBA-15 molecular sieve by taking amorphous silica alumina dry gel as a raw material and adopting 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 the solution containing the active metal component and the dispersion liquid containing the nano magnesium oxide into the slurry prepared in the step (II) to obtain mixed slurry;
(IV) filtering, washing and heat-treating the mixed slurry prepared in the step (III) to obtain a first catalyst precursor;
(V) crushing, kneading, forming, drying and roasting the first catalyst precursor prepared in the step (IV) to obtain a second catalyst precursor;
(VI) impregnating the second catalyst precursor prepared in the step (V) with an aqueous solution containing an organic auxiliary agent, and performing heat treatment on the impregnated sample to obtain the final hydrofining catalyst.
Further, 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); crystallizing to obtain Al-SBA-15 molecular sieve.
Further, in the amorphous silica alumina dry gel, the mass content of the alumina is 2% -85%, preferably 5% -82%, and more preferably 5% -75%. The mass content of alumina can be adjusted within a wide range, for example, 10%,15%,16%,18%,20%,25%,30%,32%,35%,40%,45%,50%,55%,60%,70%,75%, etc.
Further, the properties of the amorphous silica alumina dry gel are as follows: the specific surface area is 400-650 m 2 Preferably 450 to 600m 2 Per g, pore volume of 0.52 to 1.8mL/g, preferably 0.85 to 1.5mL/g, pore distribution 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. Preparing sodium aluminate solution and sodium silicate solution respectively;
b. adding part or all of the sodium silicate solution into the sodium aluminate solution, and then introducing CO 2 Controlling the reaction temperature to be 10-40 ℃, preferably 15-35 ℃ and controlling the pH value of the prepared glue to be 8-11; wherein when CO is introduced 2 When the gas amount accounts for 40% -100% of the total inlet amount, preferably 50% -80%, adding the residual sodium silicate solution;
c. the mixture is ventilated and stabilized for 10 to 30 minutes under the control of the temperature and the pH value in the step b;
d. filtering the solid-liquid mixture obtained in the step c, and washing a filter cake;
e. pulping the filter cake obtained in the step d, performing hydrothermal treatment, filtering and drying to obtain the amorphous silica-alumina dry gel; the hydrothermal treatment conditions are as follows: treating at 120-150 deg.c and 0.5-4.0 MPa for 2-10 hr.
Further, in step a, the concentration of the sodium aluminate solution is 15 to 55gAl 2 O 3 The ratio of (C/L) may be 15-35 g Al 2 O 3 The concentration of the sodium silicate solution is 50-200 g SiO 2 L, furtherThe steps can be 50 to 150g SiO 2 /L。
Further, part or all of the sodium silicate solution is added in the step b, namely 5-100 wt% of the total sodium silicate solution is added. The CO 2 The 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 the following cases: (1) Adding all sodium silicate into sodium aluminate, introducing CO 2 A gas; (2) After adding part of sodium silicate into sodium aluminate, introducing all CO 2 Gas, then adding the remaining sodium silicate solution to the mixture; (3) After adding part of sodium silicate into sodium aluminate, introducing part of CO 2 Gas, CO is introduced at the same time 2 The remaining sodium silicate solution was added while the gas was in.
Further, the slurry obtained in the step d is filtered and washed by deionized water with the temperature of 50-95 ℃ until the slurry is nearly neutral,
further, the filter cake obtained in the step e is prepared according to a solid-liquid volume ratio of 8:1 to 12:1, adding water and pulping.
Further, the drying in the step e can be performed by a conventional method, and the drying can be performed at 110-130 ℃ for 6-8 hours.
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 of the acidic solution in the step (2) is 1 to 5, preferably 1.2 to 2.3, and the mass content of the P123 triblock copolymer in the acidic aqueous solution is 0.5 to 5.0%, preferably 0.8 to 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, 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 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 ℃, preferably 90-110 ℃; the crystallization time is 10-35 h, preferably 16-24 h; the pH is controlled to be 2.0-5.0, preferably 3.2-4.8 during crystallization.
Further, after the crystallization step of step (3), the Al-SBA-15 molecular sieve may be separated from the obtained mixture by any conventionally known means, such as at least one step of filtration, washing and drying. The filtering can be suction filtration. The washing can be performed by adopting deionized water as a washing liquid. The drying may be at 80 to 150 ℃, preferably 90 to 130 ℃, and the drying time is 2 to 12 hours, preferably 3 to 6 hours. The drying may be performed at normal pressure.
Further, the molecular sieve prepared by the method can be roasted according to the requirement, so as to remove the template agent, water possibly existing and the like. The calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature of generally 450 to 600 ℃, preferably 480 to 580 ℃, further preferably 500 to 560 ℃, and a calcination time of 2 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is typically performed under an oxygen-containing atmosphere, such as air or an oxygen atmosphere.
Further, the properties of the alumina in step (II) are as follows: the specific surface area is 150-450 m 2 Preferably 230 to 340m 2 /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 nano magnesium dioxide can be 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) to the slurry prepared in the step (II) simultaneously or separately;
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 filtration and the washing are carried out by adopting the conventional means in the field, the temperature of the heat treatment is 60-180 ℃, the time is 0.5-20 h, preferably 60-120 ℃, and the time is 1-8 h, and the heat treatment is carried out under the protection of nitrogen or inert gas.
Further, in the step (V), conventional additives 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 condition is: 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 are 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 the step (VI) is one or a combination of a plurality of ribitol, D-mannitol and stachyose.
In the step (VI), the aqueous solution containing the organic auxiliary agent may be an aqueous solution in which the organic auxiliary agent is sufficiently dissolved in water.
Further, the heat treatment in the step (VI) is preferably a two-step heat treatment, wherein the temperature of the first heat treatment is 80 to 120, preferably 90 to 110 ℃, for 0.5 to 5 hours, preferably 1 to 3 hours, and the temperature of the second heat treatment is 120 to 200 ℃, preferably 150 to 180 ℃, for 0.5 to 5 hours, preferably 1 to 3 hours.
Further, the hydrofining catalyst may further contain at least one of conventional additives, such as P, B, ti, zr, wherein the content of the additive is less than 10% of the weight of the hydrofining catalyst by weight of the catalyst, and may be 0.1% -8.0%.
The invention also provides application of the hydrofining catalyst.
Further, the application is that the hydrofining catalyst is applied to shale oil hydrodenitrogenation reaction.
Further, the reaction conditions of the hydrofining catalyst applied to the shale oil hydrodenitrogenation reaction are as follows: the total pressure of the reaction is 8-16 MPa, and the liquid hourly space velocity is 0.2-8.2 h -1 Hydrogen oil volume ratio 500:1-1500: 1, the reaction temperature is 350-400 ℃.
The shale oil has the following properties: the shale oil contains more than 1wt% of nitrogen, more than 0.5wt% of sulfur and more than 0.8wt% of oxygen, and has high contents of unsaturated aromatic hydrocarbon, impurities and metals compared with conventional crude oil.
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 quantity 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, the content of strong acid is reduced, the content of medium strong acid is obviously increased, and the intrinsic activity of the catalyst is well improved; second, the Al-SBA-15 molecular sieves of the application show a regularity of the mesoporous structure, which can be characterized by the pore distribution of the molecular sieve (in particular by the pore volume fraction of pores with a pore diameter <4 nm), even in the case of very high aluminium contents, such as alumina contents higher than 7% by weight in the chemical composition of the molecular sieve. As a surmise, according to the Al-SBA-15 molecular sieve of the application, even though the mass percentage of alumina in the chemical composition of the molecular sieve is widely varied between 2% and 85%, the pore volume occupied by the pores with the pore diameter of <4nm is still less than 20% of the total pore volume, and the integrity and regularity of the mesoporous structure are maintained, which are not possessed by the Al-SBA-15 molecular sieve manufactured by the prior art. After the Al-SBA-15 molecular sieve is added, the pore channel structure of the catalyst carrier can migrate towards the mesoporous direction, which is beneficial to the reaction of macromolecular polycyclic aromatic hydrocarbon 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 catalysis, and the addition of the Al-SBA-15 mesoporous molecular sieve can obviously improve the concentration of the active metal component on the surface of the carrier, namely the dispersity of the active metal component is increased, thereby being beneficial to generating more active sites and improving the reactivity of the catalyst.
(2) The hydrofining catalyst also contains an organic aid, so that the acid property of the catalyst can be further optimized, and the denitrification activity of the catalyst is obviously improved; meanwhile, the organic auxiliary agent is added to weaken 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, so that 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 amount of medium strong acid and weak acid is 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 operation period of the device is prolonged, and the operation cost is reduced.
Drawings
FIG. 1 is an XRD pattern of an Al-SBA-15 molecular sieve obtained in example 1 of the present invention.
Detailed Description
In the present invention, al-SBA-15 molecular sieve means that aluminum atoms are introduced into SBA-15 molecular sieve, and the existence state of aluminum atoms in SBA-15 molecular sieve is not particularly limited, and part of aluminum atoms are generally distributed on the framework of SBA-15 molecular sieve.
In the invention, the determination of the L acid or the B acid adopts an infrared spectrometry, and an instrument adopts an American Nicot Fourier infrared spectrometer-6700 for determinationThe method comprises the following steps: weighing 20mg of sample with granularity smaller than 200 meshes, pressing into sheet with diameter of 20mm, placing on sample rack of absorption cell, placing 200mg of sample into instrument suspension cup, connecting absorption cell and adsorption tube, vacuumizing to vacuum degree of 4X10 -2 And (3) heating to 500 ℃ in Pa, keeping for 1 hour to remove adsorbate on the surface of the sample, cooling to room temperature, adsorbing pyridine to saturation, continuously heating to 160 ℃ and balancing for 1 hour, and then desorbing the physically adsorbed pyridine to obtain the acid amounts of the infrared total acid, the B acid and the L acid, wherein the acid amounts of the B acid and the L acid are in mmol/L.
In the invention, the medium strong acid amount is NH 3 -TPD method measurement. The apparatus was an Auto-Chem II 2920 chemisorber, a Michael Instrument company. Ammonia is used as an adsorption and desorption medium, helium is used as carrier gas, and temperature programming desorption and chromatographic analysis are adopted to obtain the acid quantity of different desorption temperature areas, wherein the ammonia desorption temperature corresponding to the acid quantity of weak acid is between 150 and 250 ℃, the ammonia desorption temperature corresponding to the acid quantity of strong acid in the temperature of 150 and 400 ℃, and the ammonia desorption temperature corresponding to the acid quantity of strong acid is between 400 and 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 the weak acid, the medium strong acid and the strong acid is the total acid amount.
In the invention, the specific surface area, pore volume and pore distribution are measured by adopting an ASAP2405 physical adsorption instrument, and the measuring method comprises the following steps: after the sample is treated, liquid N 2 As an adsorbate, the adsorption temperature was-196 ℃ and analytical tests were performed. Wherein the specific surface area is calculated by BET method, and the pore volume and pore distribution are calculated by BJH method.
In the invention, XPS characterizes metal dispersity as measured by using a Multilab 2000X-ray photoelectron spectrometer of Thermo company of America. 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 the polluted carbon peak is used as a calibration standard, the influence of the charge effect is subtracted, and the real binding energy of the sample is determined.
In the present invention, XRD was measured by using a D/max2500 type X-ray diffractometer manufactured by Japanese national institute of technology, 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 following examples and comparative examples further illustrate the operation and effect of the technical scheme of the present invention, but the present invention should not be construed as being limited to the specific examples, and the percentages are mass percentages unless otherwise specified.
Example 1
Preparation of (one) Al-SBA-15 molecular sieves
(1) Preparation of amorphous silica alumina dry gel A1 and slurry: concentration of sodium aluminate solution 20gAl 2 O 3 Concentration of sodium silicate solution 60g SiO 2 Adding 0.75L sodium aluminate solution into a colloid forming tank, adding 0.35L sodium silicate solution, controlling the reaction temperature to 20 ℃, and introducing CO with concentration of 40v% 2 Gas is introduced into CO 2 When the gas accounts for 50% of the total inlet amount, 0.20L sodium silicate solution is added while ventilation is carried out, the pH value of the gel is controlled to be 9.7, then ventilation is stabilized for 20 minutes, slurry is filtered and washed to be neutral by deionized water at 65 ℃, water is added into a filter cake according to the solid-liquid volume ratio of 12:1 for pulping, the filter cake is treated for 2 hours under the water vapor pressure of 3.5MPa at 120 ℃, and after drying for 6 hours at 120 ℃, the amorphous silicon-aluminum product A1 is obtained by crushing and sieving. Mixing the prepared amorphous silicon aluminum A1 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica alumina dry gel to the 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 the dilute hydrochloric acid solution is 0.13mol/L, the pH 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 1.6wt%;
(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 with the number of A-S-1, wherein the mass ratio of the P123 triblock copolymer to the amorphous silicon aluminum in the mixed system is 1.2:1, the crystallization temperature is 90 ℃, and the crystallization time is 20 hours; the pH is controlled to be 3.3 in the crystallization process, the drying temperature is controlled to be 100 ℃, the drying time is controlled to be 3 hours, the roasting temperature is controlled to be 550 ℃, the roasting time is controlled to be 3 hours, and the properties of the A-S-1 molecular sieve are shown in the table 1. XRD patterns of the A-S-1 molecular sieve obtained in example 1 are shown in FIG. 1, and characteristic peaks of the Al-SBA-15 molecular sieve are shown.
(II) preparing a molybdenum nickel phosphorus heteropolyacid solution A, wherein the composition MoO of the solution 3 The content of (1) is 45.5g/100mL, the content of NiO is 7.5g/100mL, the content of P is 3.5g/100mL, 10 g of nano magnesium oxide dispersion (the product produced by Hangzhou Wanshou New material Co., ltd., 30wt% of magnesium oxide in the dispersion, 30nm of particle size) is weighed, and deionized water is used for diluting to 100mL to obtain solution B; weighing 8g of A-S-1 molecular sieve, putting 92g of alumina dry rubber powder into 6L of deionized water, stirring and dissolving 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 parallel, stirring under the condition of ultrasonic power of 52Hz, treating at 45 ℃ for 40min to obtain mixed slurry, filtering and washing, and then performing heat treatment at 110 ℃ for 4 hours under the protection of nitrogen to obtain a first catalyst precursor containing nano magnesium oxide and active components; crushing a first precursor, adding 4g of sesbania powder, putting into a rolling machine, dissolving 4g of citric acid and 12.3g (concentration of 65%) of nitric acid into 125mL of deionized water to prepare an acidic solution, uniformly pouring into the rolling machine, rolling for 25min, extruding the material into paste on a strip extruder to form 1.7mm clover, drying at 130 ℃ 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 stachyose, wherein the molar ratio of stachyose to Mo atoms is 1:1, after the immersed sample is dried at room temperature, heat treatment is carried out for 3 hours at 120 ℃ and for 1 hour at 150 ℃ to obtain a final finished catalyst C-1, and main physical properties are shown in tables 2 and 3.
Example 2
Preparation of (one) Al-SBA-15 molecular sieves
(1) Preparation of amorphous silica alumina dry gel A2: concentration of sodium aluminate solution 30gAl 2 O 3 Concentration of sodium silicate working solution of 90gSiO 2 1.25L of sodium aluminate solution is put into a gel forming tank, and then 0.65L of sodium silicate is addedControlling the reaction temperature of the solution at 32 ℃, and introducing CO with the concentration of 52v percent 2 Stopping the 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 130 ℃ and the water vapor pressure of 3.9MPa, drying for 8 hours at 130 ℃, crushing and sieving to obtain an amorphous silicon aluminum product A2. Mixing the prepared amorphous silicon aluminum A2 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica alumina dry gel to the 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 the dilute hydrochloric acid solution is 0.16mol/L, the pH 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 2.0wt%;
(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 with the number of A-S-2, wherein the mass ratio of the P123 triblock copolymer to the amorphous silicon aluminum in the mixed system is 2:1, the crystallization temperature is 93 ℃, and the crystallization time is 18 hours; the pH is controlled to be 4.7 in the crystallization process, the drying temperature is controlled to be 120 ℃, the drying time is controlled to be 4 hours, the roasting temperature is controlled to be 530 ℃, and the roasting time is controlled to be 5 hours. The properties of the A-S-2 molecular sieves are shown in Table 1. The XRD pattern of the A-S-2 molecular sieve is similar to that of FIG. 1, and shows characteristic peaks of the Al-SBA-15 molecular sieve.
(II) preparing a molybdenum nickel phosphorus heteropolyacid solution A, wherein the composition MoO of the solution 3 The content of (1) was 45.5g/100mL, the content of NiO was 7.5g/100mL, and the content of P was 3.5g/100mL, 8 g of a nano magnesium oxide dispersion was weighed (same as in example 1), and diluted with deionized water to 100mL to obtain a solution B; weighing 6g of A-S-2 molecular sieve, putting 92g of alumina dry rubber powder into 6L of deionized water, stirring and dissolving to uniformly disperse the two powder bodies in the system to obtain slurry C, adding the solution A and the solution B into the slurry C in parallel, stirring under the condition of ultrasonic power of 50Hz, and stirring at 48 DEG C After 40min of treatment, mixed slurry is obtained, and then the mixed slurry is filtered and washed, and then is subjected to heat treatment for 4 hours at 110 ℃ under the protection of nitrogen, so as to obtain a first catalyst precursor containing nano magnesium oxide and active components; crushing a first catalyst precursor, adding 4g of sesbania powder, putting into a rolling machine, dissolving 4g of citric acid and 11.9g (65%) of nitric acid into 132mL of deionized water to prepare an acidic solution, uniformly pouring into the rolling machine, rolling for 25min, extruding the material into paste on a strip extruder to form 1.7mm clover, 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 ribitol in an amount to Mo atom mole ratio of 1.5:1, after the immersed sample is dried at room temperature, heat treatment is carried out for 3 hours at 110 ℃ and for 1 hour at 160 ℃ to obtain a final finished catalyst C-2, and main physical properties are shown in tables 2 and 3.
Example 3
Preparation of Al-SBA-15 molecular sieves and slurries
(1) Preparation of amorphous silica alumina dry gel A3: concentration of sodium aluminate solution 30gAl 2 O 3 Concentration of sodium silicate solution 50gSiO 2 Adding 0.75L sodium aluminate solution into a colloid forming tank, adding 0.12L sodium silicate solution, controlling the reaction temperature to 23 ℃, and introducing CO with concentration of 48v% 2 Gas is introduced into CO 2 When the gas accounts for 50% of the total inlet amount, 0.20L sodium silicate solution is added while ventilation is carried out, the pH value of the gel is controlled to be 8.8, then ventilation is stabilized for 20 minutes, slurry is filtered and washed to be neutral by deionized water at 75 ℃, water is added into a filter cake according to the solid-liquid volume ratio of 11:1 for pulping, the filter cake is treated for 2 hours under the water vapor pressure of 3.5MPa at 120 ℃, and after drying for 6 hours at 120 ℃, the amorphous silicon-aluminum product A3 is obtained by crushing and sieving. Mixing the prepared amorphous silicon aluminum A3 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica alumina dry gel to the 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 the dilute hydrochloric acid solution is 0.16mol/L, the pH 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 2.2wt%;
(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 with the number of A-S-3, wherein the mass ratio of the P123 triblock copolymer to the amorphous silicon aluminum in the mixed system is 2.5:1, the crystallization temperature is 98 ℃, and the crystallization time is 20 hours; the pH is controlled to be 4.3 in the crystallization process, the drying temperature is controlled to be 120 ℃, the drying time is 5h, the roasting temperature is controlled to be 540 ℃, and the roasting time is 5h. The properties of the A-S-3 molecular sieves are shown in Table 1. The XRD pattern of the A-S-3 molecular sieve is similar to that of FIG. 1, and shows characteristic peaks of the Al-SBA-15 molecular sieve.
(II) preparing a molybdenum nickel phosphorus heteropolyacid solution A, wherein the composition MoO of the solution 3 The content of (1) is 45.5g/100mL, the content of NiO is 7.5g/100mL, the content of P is 3.5g/100mL, 12 g of nano magnesium oxide dispersion (the product produced by Hangzhou Wanshou New material Co., ltd., 30wt% of magnesium oxide in the dispersion, particle size of 35 nm) is weighed, and deionized water is used for diluting to 100mL to obtain solution B; weighing 10g of A-S-3 molecular sieve, putting 92g of alumina dry rubber powder into 6L of deionized water, stirring and dissolving 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 parallel, stirring under the condition of ultrasonic power of 55Hz, treating at 50 ℃ for 45min to obtain mixed slurry, filtering and washing, and then performing 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 a first catalyst precursor, adding 4g of sesbania powder, putting into a rolling machine, dissolving 4g of citric acid and 12.5g (concentration of 65%) of nitric acid into 135mL of deionized water to prepare an acidic solution, uniformly pouring into the rolling machine, rolling for 25min, extruding the material into paste on a strip extruder to form 1.7mm clover, 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 ribitol, wherein ribitol The molar ratio of the amount of alcohol to Mo atoms is 2:1, after the immersed sample is dried at room temperature, heat-treating for 3 hours at 120 ℃ and heat-treating for 1.5 hours at 165 ℃ to obtain a final finished catalyst C-3, wherein the main physical properties are shown in tables 2 and 3.
Example 4
Preparation of (one) Al-SBA-15 molecular sieves
Other conditions are the same as in example 1 except that in the preparation process of the amorphous silica alumina dry gel A1 and the slurry in the step (1), the pH value of the gel is controlled to be 9.8, and the amorphous silica alumina product A4 is obtained, and finally the molecular sieve A-S-4 is prepared. The XRD pattern of the A-S-4 molecular sieve is similar to that of FIG. 1, and shows characteristic peaks of the Al-SBA-15 molecular sieve.
(II) preparing a molybdenum nickel phosphorus heteropolyacid solution A, wherein the composition MoO of the solution 3 15 g of a nano magnesium oxide dispersion solution (same as in example 1) is weighed, and diluted to 100mL by deionized water to obtain a solution B, wherein the content of 45.5g/100mL of NiO, 7.5g/100mL of NiO and 3.5g/100mL of P; weighing 12g of A-S-4 molecular sieve, putting 120g of alumina dry rubber powder into 6L of deionized water, stirring and dissolving 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 parallel, stirring under the condition of ultrasonic power of 55Hz, treating at 50 ℃ for 45min to obtain mixed slurry, filtering and washing, and then performing 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 a first catalyst precursor, adding sesbania powder 5g, dissolving citric acid 4g and nitric acid 12.8g (with concentration of 65%) in 138mL of deionized water to prepare an acidic solution, uniformly pouring into a rolling machine, rolling for 25min, extruding the material into 1.7mm clover on the extruding machine, drying at 110 ℃ for 4 hours, roasting at 450 ℃ for 3 hours to obtain a second catalyst precursor, and impregnating the second catalyst precursor with an aqueous solution containing D-mannitol, wherein the mole ratio of the dosage of the D-mannitol to Mo atoms is 0.8:1, after the immersed sample is dried at room temperature, heat-treating for 3 hours at 120 ℃ and heat-treating for 1.8 hours at 175 ℃ to obtain a final finished catalyst C-4, wherein the main physical properties are shown in tables 2 and 3.
Example 5
Preparation of (one) Al-SBA-15 molecular sieves
(1) Preparation of amorphous silica alumina dry gel A5 and slurry: concentration of sodium aluminate solution 20gAl 2 O 3 Concentration of sodium silicate solution 50gSiO 2 Adding 0.75L sodium aluminate solution into a colloid forming tank, adding 0.12L sodium silicate solution, controlling the reaction temperature at 23deg.C, and introducing 45v% CO 2 Stopping the gas, controlling the pH value of the gel to 8.8, then ventilating and stabilizing for 20 minutes, filtering the slurry, washing the slurry to be neutral by using deionized water at 75 ℃, 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 under the water vapor pressure of 3.5MPa at 120 ℃, drying the filter cake at 120 ℃ for 6 hours, and crushing and sieving the filter cake to obtain an amorphous silicon aluminum product A5. Mixing the prepared amorphous silicon aluminum A5 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica alumina dry gel to the 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 the dilute hydrochloric acid solution is 0.16mol/L, the pH 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 2.8wt%;
(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 with the number of A-S-5, wherein the mass ratio of the P123 triblock copolymer to the amorphous silicon aluminum in the mixed system is 2.5:1, the crystallization temperature is 98 ℃, and the crystallization time is 20 hours; the pH is controlled to be 4.3 in the crystallization process, the drying temperature is controlled to be 120 ℃, the drying time is 5h, the roasting temperature is controlled to be 540 ℃, and the roasting time is 5h. The properties of the A-S-5 molecular sieves are shown in Table 1. The XRD pattern of the A-S-5 molecular sieve is similar to that of FIG. 1, and shows characteristic peaks of the Al-SBA-15 molecular sieve.
(II) preparing a molybdenum nickel phosphorus heteropolyacid solution A, wherein the composition MoO of the solution 3 45.5g/100mL, niO 7.5g/100mL, and P3.5 g/100mL, referred to asTaking 8 g of nano magnesium oxide dispersion liquid (same as in example 1), and diluting to 100mL by deionized water to obtain solution B; weighing 15g of A-S-2 molecular sieve, putting 125g of alumina dry gel powder into 8L of deionized water, stirring and dissolving 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 parallel, stirring under the condition of ultrasonic power of 53Hz, treating at 42 ℃ for 40min to obtain mixed slurry, filtering and washing, and then performing 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 a first catalyst precursor, adding sesbania powder 5g, putting into a rolling machine, dissolving citric acid 5g and nitric acid 13.5g (with concentration of 65%) into 141mL of deionized water to prepare an acidic solution, uniformly pouring into the rolling machine, rolling for 25min, extruding into clover with the thickness of 1.7mm on a strip extruder, 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 mole ratio of the D-mannitol to Mo is 0.5:1, the mole ratio of stachyose to Mo is 0.8:1, after the immersed sample is dried at room temperature, carrying out heat treatment for 3 hours at 130 ℃ and 1.5 hours at 155 ℃ to obtain a final finished catalyst C-5, wherein 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 gel powder and 50g of macroporous aluminum oxide dry gel powder, adding 5g of citric acid and sesbania powder respectively, and uniformly mixing. 155g of a dilute aqueous nitric acid solution, 12.5g (65% strength) by mass of nitric acid, were then added homogeneously. Kneading the materials for 25min, rolling for 25min, and extruding strips with clover orifice plate with diameter of 1.7 mm. Drying at 120 deg.C for 4h, and roasting at 550 deg.C for 4h. The calcined support was designated as Z-1.
(2) Catalyst preparation
The carrier Z-1 is impregnated with the impregnating solution containing Mo, ni and P in equal volume, dried at room temperature, dried at 110 ℃ for 4h, baked at 435 ℃ for 3h, and finally the obtained catalyst is marked as C-6. The catalyst properties are shown in tables 2 and 3.
Comparative example 2
Respectively weighing a template agent triblock copolymer P123 and silicon source ethyl orthosilicate, wherein the mass of the template agent P123 is 5.5g, and the mass of the ethyl orthosilicate is 10.2g; adding a template agent and a silicon source into an HCl solution with the pH of 2.8, and fully stirring for 30 hours at the temperature of 28 ℃; standing and crystallizing the stirred mixture for 20 hours at 120 ℃, washing with deionized water, and drying to obtain SBA-15. The obtained SBA-15 molecular sieve is pulped, the solid-liquid ratio is 1:10, then the molecular sieve is added into hydrochloric acid solution containing 23g of aluminum isopropoxide, the temperature is raised to 100 ℃, the stirring is carried out for 20 hours, the molecular sieve is dried at 60 ℃ overnight after filtering and washing, and the molecular sieve is roasted at 550 ℃ for 5 hours, thus obtaining mesoporous material A-S-8, and the properties are shown in table 1.
The catalyst was prepared in the same manner as in example 1 except that A-S-1 was changed to A-S-8 catalyst number C-7. The catalyst properties are shown in tables 2 and 3.
Comparative example 3
6.2g of P123 is added into 600ml of 0.18mol/L hydrochloric acid solution, the temperature is raised to 26 ℃ and then the mixture is stirred for 6 hours at constant temperature, and after P123 is completely dissolved, the solution is in a transparent state. Adding 5.2 and gY molecular sieve slurry, controlling the pH value to be 3.3, stirring at constant temperature for reaction for 6 hours, and heating to 98 ℃ for hydrothermal crystallization for 24 hours. Then filtering, washing, drying at 120 ℃ for 6 hours, roasting at 550 ℃ for 6 hours to obtain the Al-SBA-15 mesoporous molecular sieve with the number of A-S-9, and the properties are shown in Table 1.
The catalyst was prepared in the same manner as in example 1 except that A-S-1 was changed to A-S-9 catalyst No. C-8. The catalyst properties are shown in tables 2 and 3.
Comparative example 4
Roasting and activating kaolin for 4 hours at 700 ℃, weighing 12g of the roasted kaolin, soaking the kaolin in 6mol/L hydrochloric acid for 4 hours, and then filtering, washing with deionized water to be neutral and drying; roasting the dried sample at 900 ℃ for 2 hours; then the mixture is put into 5mol/L NaOH alkali solution to react for 3 hours (the temperature is 160 ℃ and the pressure is 0.5 MPa) under high temperature and high pressure, and the pH value is regulated to be 14.0 after the reaction is completed. Then the mixture is added into a mixed solution of a surfactant and acid dropwise (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 the mixture is filtered, washed and dried and then baked for 6 hours at 550 ℃ in a muffle furnace, so that mesoporous material A-S-10 is obtained, and the properties are shown in table 1.
The catalyst was prepared in the same manner as in example 1 except that A-S-1 was changed to A-S-10 and the catalyst number was 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 P123 is completely dissolved; adding 8.5g of tetraethoxysilane into a hydrochloric acid solution containing P123, stirring for 4 hours, adding aluminum nitrate to enable the silicon aluminum molar ratio to be 35, continuously stirring 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 at 60 ℃ overnight, and roasting at 550 ℃ for 6 hours to obtain the mesoporous material A-S-11, wherein the properties are shown in the table 1.
The catalyst was prepared in the same manner as in example 1 except that A-S-1 was changed to A-S-11 and the catalyst was designated as C-10. The catalyst properties are shown in tables 2 and 3.
TABLE 1 Al-SBA-15 molecular sieve Properties
Project A-S-1 A-S-2 A-S-3 A-S-4 A-S-5
Specific surface area, m 2 /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
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
Pore distribution, percent
＜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, below
Project A-S-8 A-S-9 A-S-10 A-S-11
Specific surface area, m 2 /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
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
Pore distribution, percent
＜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 catalysts
Catalyst numbering C-1 C-2 C-3 C-4 C-5
Composition of the composition
MoO 3 ，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 (C)
Specific surface area, m 2 /g 223 225 228 226 228
Pore volume, mL/g 0.36 0.37 0.38 0.35 0.34
Acid distribution
Weak acid, percent 31.37 35.75 37.58 34.58 33.65
Medium strong acid, percent 58.62 55.23 54.30 56.89 57.26
Strong acid,% 10.01 9.02 8.12 8.53 9.09
Dispersity of
Mo/Al 0.172 0.178 0.180 0.176 0.178
Ni/Al 0.07 0.08 0.07 0.08 0.07
Continuous table 2
Catalyst numbering C-6 C-7 C-8 C-9 C-10
Composition of the composition
MoO 3 ，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 (C)
Specific surface area, m 2 /g 186 212 215 209 218
Pore volume, mL/g 0.30 0.31 0.32 0.33 0.33
Acid distribution
Weak acid, percent 33.12 37.44 37.62 36.57 35.62
Medium strong acid, percent 38.20 48.36 46.02 47.38 48.03
Strong acid,% 28.68 14.20 16.36 16.05 16.35
Dispersity of
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 comparative catalyst strength for 2000 hours of operation
Catalyst numbering C-1 C-2 C-3 C-4 C-5 C-6
New agent crush strength, 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
Catalyst activity evaluation experiments of examples and comparative examples were performed on a 100mL small fixed bed hydrogenation unit, and the catalyst was presulfided before evaluation. The catalyst evaluation condition is that the total pressure of the reaction is 14.5MPa, and the liquid hourly space velocity is 0.2h -1 Hydrogen oil volume ratio 1200:1, the reaction temperature was 383 ℃. The properties of the raw oil for activity evaluation experiments are shown in Table 4, and the results of activity evaluation are shown in Table 5.
TABLE 4 Properties of raw oil
Raw oil name Shale oil full 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.)/mm 2 ·s -1 3.471
Viscosity (100 ℃ C.)/mm 2 ·s -1 11.70
Condensation point/. Degree.C 35
Flash point/. Degree.C (closed)
Carbon residue, 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
Mass spectrum composition, wt%
Paraffin hydrocarbons 19.3
Total cycloalkane 27.1
Total aromatic hydrocarbon 32.7
Total gum 20.9
TABLE 5 evaluation results of Activity
Catalyst numbering Nitrogen content, μg.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 example 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, m 2 /g 512 537 528 535 519
Pore volume, mL/g 1.18 1.23 1.20 1.26 1.19
Pore distribution, percent
4～15nm 88 86 87 92 93
＞15nm 3 4 3 3 2

Claims (24)

1. A hydrofining catalyst, characterized in that: 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 alumina;
the organic auxiliary agent is one or a combination of a plurality of ribitol, D-mannitol and stachyose;
the pore distribution of the Al-SBA-15 molecular sieve comprises: the pore volume occupied by the pores with the pore diameter of <4nm is less than 20% of the total pore volume; in the Al-SBA-15 molecular sieve, the ratio of B acid to L acid is below 1; the medium strong acid content is 0.6-1.0 mL/g;
the preparation method of the hydrofining catalyst comprises the following steps:
(I) Preparing an Al-SBA-15 molecular sieve by taking amorphous silica alumina dry gel as a raw material and adopting 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 the solution containing the active metal component and the dispersion liquid containing the nano magnesium oxide into the slurry prepared in the step (II) to obtain mixed slurry;
(IV) filtering, washing and heat-treating the mixed slurry prepared in the step (III) to obtain a first catalyst precursor;
(V) crushing, kneading, forming, drying and roasting the first catalyst precursor prepared in the step (IV) to obtain a second catalyst precursor;
(VI) impregnating the second catalyst precursor prepared in step (V) with an aqueous solution containing an organic additive, and heat-treating the impregnated sample to obtain a hydrofined catalyst;
a process for preparing an Al-SBA-15 molecular sieve in step (I) comprising:
(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); crystallizing to obtain Al-SBA-15 molecular sieve.
2. The hydrofinishing catalyst according to claim 1, wherein: the hydrofining catalyst has the following properties: the specific surface area is 180-240 m 2 Per g, the 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.
3. The hydrofinishing catalyst according to claim 2, wherein: the hydrofining catalyst has the following properties: the content of the medium strong acid accounts for 53% -63% of the total acid content.
4. The hydrofinishing catalyst according to claim 1, wherein: the active metal component is a VIII group metal and a VIB group metal, the VIII group metal is Co and/or Ni, and the VIB group metal is W and/or Mo; the weight of the hydrofining catalyst is taken as a reference, the content of the metal in the VIII group is 1-15 wt% based on the oxide, and the content of the metal in the VIB group is 10-30 wt% based on the oxide.
5. The hydrofining catalyst according to claim 4, wherein: the weight of the hydrofining catalyst is taken as a reference, the content of the metal in the VIII group is 3-10 wt% based on the oxide, and the content of the metal in the VIB group is 15-25 wt% based on the oxide.
6. The hydrofining catalyst according to claim 4, wherein: 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 oxide, and the content of the nano magnesium oxide is 1% -6%; in the hydrofining catalyst, the mole ratio of the content of the organic auxiliary agent to the atom of the metal in the VIB group is 0.01:1 to 12:1.
7. The hydrofining catalyst according to claim 6, wherein: in the hydrofining catalyst, the mole ratio of the content of the organic auxiliary agent to the atom of the metal in the VIB group is 0.01:1 to 10:1.
8. the hydrofinishing catalyst according to claim 1, wherein: in the carrier, the weight content of the Al-SBA-15 molecular sieve is 2% -20%, and the weight content of the alumina is 80% -98%.
9. The hydrofinishing catalyst of claim 8, wherein: in the carrier, the weight content of the Al-SBA-15 molecular sieve is 3% -12%, and the weight content of the alumina is 88% -97%.
10. The hydrofinishing catalyst according to claim 1, wherein: the pore distribution of the Al-SBA-15 molecular sieve comprises: the pore volume occupied by the pores with the pore diameter of <4nm is less than 15% of the total pore volume; in the Al-SBA-15 molecular sieve, the medium strong acid content is 0.7-0.9 mL/g.
11. The hydrofinishing catalyst according to claim 1, wherein: in the Al-SBA-15 molecular sieve, the mass content of the alumina is 2% -85%.
12. The hydrofinishing catalyst of claim 11, wherein: in the Al-SBA-15 molecular sieve, the mass content of the alumina is 5% -82%.
13. The hydrofinishing catalyst of claim 11, wherein: in the Al-SBA-15 molecular sieve, the mass content of the alumina is 5% -75%.
14. A process for preparing a hydrofinishing catalyst according to any one of claims 1 to 13, comprising:
(I) Preparing an Al-SBA-15 molecular sieve by taking amorphous silica alumina dry gel as a raw material and adopting 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 the solution containing the active metal component and the dispersion liquid containing the nano magnesium oxide into the slurry prepared in the step (II) to obtain mixed slurry;
(IV) filtering, washing and heat-treating the mixed slurry prepared in the step (III) to obtain a first catalyst precursor;
(V) crushing, kneading, forming, drying and roasting the first catalyst precursor prepared in the step (IV) to obtain a second catalyst precursor;
(VI) impregnating the second catalyst precursor prepared in the step (V) with an aqueous solution containing an organic auxiliary agent, and performing heat treatment on the impregnated sample to obtain the hydrofining catalyst.
15. The method of claim 14, wherein: a process for preparing an Al-SBA-15 molecular sieve in step (I) comprising:
(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); crystallizing to obtain Al-SBA-15 molecular sieve.
16. The method of claim 14, wherein: in the step (II), the mass concentration of the nano magnesium oxide 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.
17. The method of claim 14, wherein: the properties of the alumina in step (II) are as follows: the specific surface area is 150-450 m 2 /g; the pore volume is 0.4-1.4 mL/g, and the average pore diameter is 8-14 nm.
18. The method of claim 17, wherein: the properties of the alumina in step (II) are as follows: the specific surface area is 230-340 m 2 /g; the pore volume is 0.8-1.2 mL/g.
19. The method of claim 14, 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; the temperature is controlled at 20-80 ℃ and the stirring time is 10-80 min.
20. The method of claim 19, wherein: the power of the ultrasonic wave is 20-60 Hz; the temperature is controlled between 40 and 60 ℃, and the stirring time is 20 to 60 minutes.
21. The method of claim 14, wherein: the heat treatment in the step (VI) is two-step heat treatment, wherein the temperature of the first heat treatment is 80-120 ℃ for 0.5-5 h, and the temperature of the second heat treatment is 120-200 ℃ for 0.5-5 h.
22. The method of claim 21, wherein: the heat treatment in the step (VI) is two-step heat treatment, wherein the temperature of the first heat treatment is 90-110 ℃, the time is 1-3 h, and the temperature of the second heat treatment is 150-180 ℃ and the time is 1-3 h.
23. The application of the hydrofining catalyst in the hydrodenitrogenation reaction of shale oil is characterized in that: the catalyst is a hydrofinishing catalyst according to any one of claims 1 to 13 or prepared according to the method of any one of claims 14 to 22.
24. The use according to claim 23, characterized in that: the shale oil has the following properties: the nitrogen content is more than 1wt%, the sulfur content is more than 0.5wt%, and the oxygen content is more than 0.8wt%.
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