CN114433177B - Catalyst carrier, hydrogenation catalyst and method for producing low BMCI value tail oil and high-yield aviation kerosene - Google Patents

Catalyst carrier, hydrogenation catalyst and method for producing low BMCI value tail oil and high-yield aviation kerosene Download PDF

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CN114433177B
CN114433177B CN202011188369.1A CN202011188369A CN114433177B CN 114433177 B CN114433177 B CN 114433177B CN 202011188369 A CN202011188369 A CN 202011188369A CN 114433177 B CN114433177 B CN 114433177B
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pore
catalyst
carrier
pore diameter
hours
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CN114433177A (en
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董松涛
梁家林
杨平
赵阳
莫昌艺
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
    • B01J35/617—500-1000 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
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • 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
    • 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
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/308—Gravity, density, e.g. API
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a hydrogenation catalyst and a preparation method thereof, wherein the hydrogenation catalyst comprises a carrier and an active metal component; the carrier has a bimodal pore structure and contains a Y-type molecular sieve; in the bimodal pore structure, the pore diameter of a macropore which can be several pores is in the range of 300-750 nm, the pore diameter of a micropore which can be several pores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropore which can be several pores to the pore diameter of the micropore which can be several pores is 45-95; the ratio of the pore volume of the large pore to the pore volume of the small pore is 3-10, the pore volume of the large pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the large pore, and the pore volume of the small pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the small pore. The hydrogenation catalyst is suitable for hydrotreating, has higher activity stability and aviation kerosene yield, and is suitable for producing low BMCI value tail oil and high aviation kerosene yield.

Description

Catalyst carrier, hydrogenation catalyst and method for producing low BMCI value tail oil and high-yield aviation kerosene
Technical Field
The invention relates to the field of catalysts or carriers, in particular to a catalyst carrier, a hydrogenation catalyst and a method for producing low BMCI value tail oil and high-yield aviation kerosene.
Background
Along with the increasing heavy and inferior crude oil, the conversion of heavy distillate oil becomes a difficult problem of oil refining catalysts and technologies. Hydrocracking is one of the key technologies for lightening oil products, and in the process of heavy oil products, polycyclic hydrocarbons, especially naphthenes and aromatics with more than three rings, accumulate in circulating oil, so that the activity of the catalyst is reduced, the operation period is shortened, and the like.
The processing capacity of the heavy distillate oil of the hydrocracking technology is improved, and the heavy distillate oil is mainly used for a hydrocracking catalyst. The hydrocracking catalyst is a double-function catalyst and contains an acidic component and a hydrogenation active component, and in order to meet different requirements on hydrocracking products, the acidic component and the hydrogenation active component in the catalyst need to be adaptively modulated.
The acidic components can be classified into molecular sieves and amorphous silica alumina according to the degree of crystallization. Molecular sieves are used in catalysts that require more acid centers and are highly reactive. Amorphous silica alumina is commonly used in catalysts requiring lower acid densities, such as high middle distillate selectivity hydrocracking catalysts and hydroisomerization catalysts. However, a general disadvantage of amorphous silica alumina materials is the relatively low cracking activity.
For hydrocracking catalysts, the improvement of catalyst performance, on the one hand, requires further improvement of hydrogenation performance; on the other hand, suitable acidic components are required to enable the cracking or isomerism properties to be matched to the desired product. However, the space for performance adjustment of the hydrogenation component is limited, and although noble metal can be used as the hydrogenation component, sulfur-containing raw materials cannot be processed generally, so that the hydrogenation component of the industrial hydrocracking catalyst generally selects non-noble metal as the hydrogenation component, the hydrogenation activity of the non-noble metal is lower than that of the noble metal, the requirement cannot be met, and how to improve the hydrogenation performance of the catalyst is a problem to be solved by the partial hydrocracking catalyst.
For processing heavy fractions such as residuum, hydrogenation catalysts generally have bimodal pore structures, with typical pore locations ranging from 5 to 20nm or from 10 to 30nm, from 100 to 300nm, and from 300 to 500nm. Because of the larger molecular size of residuum molecules, the catalyst generally does not contain acidic components, which would otherwise severely impact catalyst life.
CN104226322B provides a heavy oil hydrotreating catalyst, preparation and use thereof. The pore volume of the pores with the diameter of 10-30 nm is controlled to be 55-80% of the total pore volume, the pore volume of the pores with the diameter of 300-500 nm is controlled to be 10-35% of the total pore volume, and the catalyst provided by the patent has better hydrodeasphaltene and demetallization performance when being used for heavy oil hydrotreatment. Chinese patent CN101433842A provides a hydrogenation catalyst and a preparation method thereof, and takes Pd and Ag bimetallic as active components, and is characterized in that the catalyst has bimodal pore distribution, the most probable radius of a small pore part is 2-50 nm, and the most probable radius of a large pore part is 100-500 nm. The catalyst has good hydrogenation activity and selectivity, large ethylene increment and remarkable economic benefit because of the bimodal pore distribution. The catalyst can also improve the pH value of the surface of the carrier, effectively reduce the generation of green oil and prolong the service life of the catalyst. CN108236939a provides an alumina carrier containing mesopores/macropores and a preparation method thereof. The pore diameter of the carrier is in bimodal distribution, wherein the mesoporous volume of 10-50 nm accounts for 10-50% of the total pore volume, the macroporous volume of 50-200 nm accounts for 50-90% of the total pore volume, and the carrier uses nitrile rubber emulsion as a pore expanding agent.
Most of these patents are used for residuum hydrogenation or as a carrier for a protective agent, divided into two or more pore size channels. But for oils that are heavier than conventional VGO, but lighter than resid, do not need to have too many macropores. Thus, there is a need for a suitable hydrogenation catalyst for the hydro-upgrading of heavy distillate oils.
Disclosure of Invention
The invention aims to provide a method for producing low BMCI tail oil and high-yield aviation kerosene by hydro-upgrading heavy distillate oil.
In order to achieve the above object, the first aspect of the present invention provides a carrier for preparing a hydrogenation catalyst, the carrier having a bimodal pore structure and containing 1 to 30wt% of a Y-type molecular sieve; in the bimodal pore structure, the pore diameter of a macropore which can be several pores is in the range of 300-750 nm, the pore diameter of a micropore which can be several pores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropore which can be several pores to the pore diameter of the micropore which can be several pores is 45-95; the ratio of the pore volume of the large pore to the pore volume of the small pore is 3-10, the pore volume of the large pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the large pore, and the pore volume of the small pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the small pore.
In a second aspect, the present invention provides a process for producing a carrier for a hydrogenation catalyst, the process comprising:
s1, mixing pseudo-boehmite, amorphous silicon aluminum oxide, a Y-type molecular sieve, carboxymethyl cellulose and sesbania powder to obtain mixed powder;
s2, mixing the mixed powder with a nitric acid solution, kneading and extruding to obtain an extruded strip;
s3, carrying out first drying and first roasting on the extruded strip.
In a third aspect the present invention provides a hydrogenation catalyst comprising the support and an active metal component as described above.
In a fourth aspect, the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:
SS1, impregnating the carrier of the invention with an aqueous solution containing a hydrogenation-active component compound to obtain an impregnated carrier;
SS2, subjecting the impregnated support to a second drying and a second calcination.
The fifth aspect of the invention provides a method for producing low BMCI tail oil and high-yield aviation kerosene by hydro-upgrading heavy distillate, wherein the heavy distillate and hydrogen are contacted with the hydrogenation catalyst under hydrogenation conditions.
Through the technical scheme, the hydrogenation catalyst provided by the invention comprises the carrier and the active metal component, wherein the carrier has a bimodal pore structure, the hydrogenation catalyst is suitable for hydrotreating, has higher activity stability and aviation kerosene yield, and is suitable for producing low BMCI value tail oil and high-yield aviation kerosene.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In a first aspect the present invention provides a support for use in the preparation of a hydrogenation catalyst, the support having a bimodal pore structure and comprising from 1 to 30wt% of a Y-type molecular sieve; in the bimodal pore structure, the pore diameter of a macropore which can be several pores is in the range of 300-750 nm, the pore diameter of a micropore which can be several pores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropore which can be several pores to the pore diameter of the micropore which can be several pores is 45-95; the ratio of the pore volume of the large pore to the pore volume of the small pore is 3-10, the pore volume of the large pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the large pore, and the pore volume of the small pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the small pore.
Bimodal pore in the present invention means that two distinct peaks appear on the pore distribution curve of mercury intrusion or BET, where the location of the peak's point of attachment becomes accessible to the pore size. The peaks mentioned in the present invention may have a symmetrical distribution or an asymmetrical distribution, and the present invention does not limit the peak type.
Kong Rongbi in the invention is the ratio of pore volume to pore volume, the units are mL/g, and the ratio is a dimensionless value. Kong Rongbi is 3-10, which means that the bimodal pore has a large pore and also has opposite small pores, the pore volume of the large pore and the small pore which can reach 50% of the pore diameter coverage range is calculated respectively, the ratio of the pore volume is 3-10, wherein the pore volume related to the small pore is larger.
The up and down 50% coverage of the aperture in the present invention means that the total coverage of a given accessible pore aperture, for example, an accessible pore aperture of 10nm, is 5-15 nm, and the up and down 50% coverage is the pore volume accumulation within the range of the aperture.
Macropores in the present invention refer to the pores of the support or catalyst, most or most of which are above 3.0nm, or greater than 5.0nm, but it is not excluded that some of the pores fall below 5.0 nm.
The most probable pore diameter in the present invention means a pore diameter corresponding to the maximum value of dV/dr in a distribution curve of the derivative of specific pore volume to pore diameter (i.e., dV/dr) with pore diameter obtained when measuring the pore structure of a sample by the BET method.
As a preferred embodiment of the present invention, in the carrier, the pore diameter of the macropores may be in the range of 450 to 700nm, and the pore diameter of the micropores may be in the range of 5 to 9 nm; the pore volume of the macropores can account for 15-20% of the total pore volume of the carrier.
The hole concentration in the present invention means: when the pore structure of the sample is measured by the BET method, the obtained distribution curve of the differentiation of the specific pore volume to the pore diameter along with the pore diameter has the most probable dV/dr value corresponding to the pore diameter. The larger this value, the higher the pore size concentration of the porous support. According to the present invention, when there are a plurality of peaks in the distribution curve of dV/dr with pore diameter, the ratio of the peak height of each peak to the half-width of the peak should satisfy the above-mentioned requirement. As a preferred embodiment of the present invention, the pore concentration value of the small pores is not less than 0.5, preferably not less than 0.75.
According to a first aspect of the present invention, the support may contain a non-amorphous mesoporous acidic material and a Y-type molecular sieve; the non-amorphous mesoporous acidic material may be well known to those skilled in the art and may include, for example, a two-component oxide comprising at least one of alumina-silica, alumina-titania, alumina-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, and titania-zirconia; preferably, the non-amorphous mesoporous acidic material is selected from at least one of silicon aluminum composite oxide, titanium aluminum composite oxide, and titanium silicon composite oxide. As a preferred embodiment, the non-amorphous mesoporous acidic material is a silicon aluminum composite oxide.
In a second aspect, the present invention provides a process for preparing a support for a hydrogenation catalyst, the process comprising:
s1, mixing pseudo-boehmite, amorphous silicon aluminum oxide, a Y-type molecular sieve, carboxymethyl cellulose and sesbania powder to obtain mixed powder;
s2, mixing the mixed powder with a nitric acid solution, kneading and extruding to obtain an extruded strip;
s3, carrying out first drying and first roasting on the extruded strip.
According to the second aspect of the present invention, in step S1, the weight ratio of the pseudo-boehmite, the amorphous silica-alumina, the Y-type molecular sieve, the carboxymethyl cellulose, and the sesbania powder may be 10 to 65: 25-80: 1-30: 0.1 to 3.0:2.5 to 3.5; preferably 15 to 60: 30-75: 2 to 25:0.2 to 2.8:2.8 to 3.2; in step S2, the amount of the nitric acid solution may be 50 to 130mL per 100g of the mixed powder.
According to a second aspect of the invention, the feature of the pseudo-boehmite may include: siO (SiO) 2 The content of (C) is less than 0.1wt%, fe 2 O 3 Less than 0.01wt%, na 2 The content of O is less than 0.15wt%, the content of water is less than 3wt%, and the ignition loss is 32-38 wt%; the pore volume of the pseudo-thin aluminum water stone is 0.60-1.1mL/g, and the specific surface is 220-310m 2 /g; the amorphous silicon aluminum oxide may be characterized as comprising: siO (SiO) 2 The content of (C) is 15-55wt%, al 2 O 3 The content of (2) is 45-85wt%, and the bulk density is 250-450 g/L; the Y-type molecular sieve may be characterized as comprising: the unit cell constant is 2.425-2.465 nm, and the crystallinity is 50-90%; specific surface area of 550-750 m 2 /g; pore volume is 0.32-0.56 mL/g, sodium oxide content is 0.05-0.30wt%; the sodium content of the 2% aqueous solution of the carboxymethyl cellulose is less than 2.0wt%; the mass concentration of the nitric acid solution can be 0.3-2.5%.
According to a second aspect of the present invention, in step S2, the mixing conditions may include: the temperature is 10-40 ℃ and the time is 1-10 minutes; in step S3, the first drying condition may include: the temperature is 100-130 ℃ and the time is 3-20 hours; the conditions of the first firing may include: the temperature is 400-600 ℃, the time is 2-10 hours, and the air flow is 20-50L/h.
A third aspect of the present invention provides a hydrogenation catalyst comprising the support and active metal component described above.
According to a third aspect of the invention, the active metal component may be selected from the group consisting of group VIII and/or group VIB metal elements; preferably, the group VIII metal element may be cobalt and/or nickel, and the group VIB metal element may be molybdenum and/or tungsten.
According to the third aspect of the invention, the group VIB metal content may be 20 to 30 wt.% and the group VIII metal content may be 1.5 to 8.5 wt.% based on the total catalyst and calculated as oxide.
In a fourth aspect, the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:
SS1, impregnating the carrier by using an aqueous solution containing a hydrogenation active component compound to obtain an impregnated carrier;
SS2, subjecting the impregnated support to a second drying and a second calcination.
According to a fourth aspect of the present invention, the hydrogenation-active component compound may comprise a group VIII metal-containing compound and/or a group VIB metal-containing compound; preferably, the group VIII metal-containing compound may be at least one of nitrate, acetate, carbonate, chloride, and complex of nickel and cobalt; the group VIB metal-containing compound can include at least one of molybdic acid, paramolybdic acid, molybdate, para-molybdate, tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate, and ethyl metatungstic acid.
According to the fourth aspect of the present invention, the aqueous solution containing the hydrogenation-active component compound may contain ammonium sulfate.
According to a fourth aspect of the present invention, in step SS1, the conditions of the impregnation may include: the soaking temperature is 5-150 ℃ and the soaking time is 0.5-12 hours; in step SS2, the conditions of the first drying process may include: the drying temperature is 80-350deg.C, preferably 100-300deg.C; the drying time is 0.5 to 24 hours, preferably 1 to 12 hours; the conditions of the second firing may include: the roasting temperature is 360-700 ℃, preferably 400-650 ℃; the calcination time is 0.2 to 12 hours, preferably 1 to 10 hours.
The fifth aspect of the invention provides a method for producing low BMCI tail oil and high-yield aviation kerosene by hydro-upgrading heavy distillate, wherein the heavy distillate and hydrogen are contacted with the hydrogenation catalyst under hydrogenation conditions.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way. In the examples and comparative examples of the present invention, the dry basis was determined by calcining the sample at 600℃for 4 hours.
Example 1
37.21g of CL-A (from catalyst Kaolin Co., dry basis 64.5%) and 91.59g of Si-Al material Siral40 (from catalyst Kaolin Co., SASOL production, silica content 40.3% and dry basis 79.7%) were taken, and Y-type molecular sieve USY-A (from catalyst Kaolin Co., unit cell constantCrystallinity 84.7%) 3.68g, carboxymethyl cellulose A (M450, import split charging) 0.25g, sesbania powder 3g, and mixing to obtain mixed powder. 1.4mL of concentrated nitric acid was added to 122mL of water and stirred at room temperature for 5 minutes. Mixing nitric acid solution with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adopting +.>The extruded strips are obtained by drying the extruded strips at 120 ℃ for 6 hours, the dried strips are taken and put into a roasting furnace, the dried strips are treated at 550 ℃ for 3 hours, the air flow is kept at 30L/h, the temperature is reduced to room temperature, and the dried strips are taken out and marked as carrier AC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the content of tungsten oxide of 23 weight percent and the content of nickel oxide of 5.5 weight percent in the catalyst, adding 1.30g of ammonium sulfate, adjusting the water quantity, and impregnating the prepared carrier AC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 440℃for 3 hours, and the air flow rate was maintained at not less than 27.5 cubic meters/(kg carrier. Hr) during calcination, to thereby obtain a catalyst AS.
Example 2
52.71g of CL-A (from catalyst Kaolin Co., dry basis 64.5%) and 72.77g of Si-Al material Siral40 (from catalyst Kaolin Co., SASOL production, silica content 40.3% and dry basis 79.7%) were taken, and Y-type molecular sieve USY-B (from catalyst Kaolin Co., unit cell constantCrystallinity 81.4%) 9.59g, carboxymethyl cellulose B (Shandong Heda Co., ltd.) 0.5g, sesbania powder 3g, and mixing to obtain a mixed powder. 2.8mL of concentrated nitric acid was added to 97mL of water and stirred at room temperature for 5 minutes. Mixing nitric acid solution with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adopting +.>The extruded strips are obtained by a trilobal orifice plate, dried at 115 ℃ for 6 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 2.5 hours at 600 ℃, the air flow is kept at 35L/h, and the dried strips are taken out after being cooled to room temperature and marked as carrier BC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the tungsten oxide content of 25 wt% and the nickel oxide content of 7 wt% in the catalyst, adding 2.30g of ammonium sulfate, adjusting the water quantity, and impregnating the prepared carrier BC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 450℃for 3 hours, and the air flow rate was maintained at not less than 35 cubic meters/(kg carrier. Hr) during calcination, to thereby obtain a catalyst BS.
Example 3
25.68g of SB (from catalyst Kaolin Co., ltd., dry basis 74%) and 77.68g of Si-Al material SA-1 (from zipcocene catalyst plant, silica content 28.8% and dry basis 81.1%) were taken, and Y-type molecular sieve USY-C (from catalyst Kaolin Co., ltd., unit cell constantCrystallinity 73.5%) 21.15g, carboxymethyl cellulose A #M451, inlet split charging) 0.75g, sesbania powder 3g, and mixing to obtain mixed powder. 1.0mL of concentrated nitric acid was added to 105mL of water and stirred at room temperature for 5 minutes. Mixing nitric acid solution with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adopting +.>The extruded strips are obtained by a trilobal orifice plate, dried at 125 ℃ for 5 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 3 hours at 580 ℃, the air flow is kept at 40L/h, and the dried strips are taken out after being cooled to room temperature and marked as carrier CC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the content of tungsten oxide of 26 weight percent and the content of nickel oxide of 4 weight percent in the catalyst, adding 3.00g of ammonium sulfate, adjusting the water quantity, and impregnating the prepared carrier CC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, and then calcined at 430℃for 3 hours, with the air flow rate kept at not less than 20 cubic meters/(kg carrier. Hr) during the calcination, to thereby obtain the catalyst CS.
Example 4
59.46g of SB (from catalyst Kaolin Co., ltd., dry basis 74%) and 53.55g of Si-Al material SA-2 (from zipcocene catalyst plant, silica content 32.6% and dry basis 80.3%) were taken, and Y-type molecular sieve USY-B (from catalyst Kaolin Co., ltd., unit cell constant was taken)Crystallinity 81.4%) 15.59g, carboxymethyl cellulose B (Shandong Heda Co., ltd.) 1g, sesbania powder 3g, and mixing to obtain a mixed powder. 2.4mL of concentrated nitric acid was added to 72mL of water and stirred at room temperature for 5 minutes. Mixing nitric acid solution with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adopting +.>The extruded strips are dried at 130 ℃ for 4 hours to obtain dry strips, the dry strips are taken and put into a roasting furnace to be treated at 560 ℃ for 3 hours, and the air flow is kept35L/h, cooled to room temperature and taken out, and designated as carrier DC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (both from a long-term catalyst factory) according to the content of tungsten oxide in the catalyst being 24 wt% and the content of nickel oxide being 5wt%, adding 4.20g of ammonium sulfate, adjusting the water quantity, and impregnating the prepared carrier DC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 440℃for 3 hours, and the air flow rate was maintained at not less than 25 cubic meters/(kg carrier. Hour) during calcination, to thereby obtain catalyst DS.
Example 5
38.41g of USA (from the mill of the metallocene catalyst, 75.5% dry basis), 76.34g of Si-Al material SA-3 (from the mill of the metallocene catalyst, 39.7% silica content, 78.6% dry basis) and 76.34g of Y-type molecular sieve USY-A (from the company of the catalyst, long-term Co., ltd., unit cell constant were taken13.50g of carboxymethyl cellulose A (M452, import split charging) 1.25g and sesbania powder 3g, and mixing to obtain mixed powder. 0.3mL of concentrated nitric acid was added to 100mL of water and stirred at room temperature for 5 minutes. Mixing nitric acid solution with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adopting +.>The extruded strips are obtained by a trilobal orifice plate, dried at 105 ℃ for 10 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 2 hours at 620 ℃, the air flow is kept at 45L/h, and the dried strips are taken out after being cooled to room temperature and marked as a carrier EC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are all taken from a kaolin catalyst factory) according to the tungsten oxide content of 25.5 weight percent and the nickel oxide content of 3.5 weight percent in the catalyst, adding 5.00g of ammonium sulfate, adjusting the water quantity, and impregnating the prepared carrier EC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 425℃for 3 hours, and the air flow rate was maintained at not less than 17.5 cubic meters/(kg carrier. Hr) during calcination, to thereby obtain a catalyst ES.
Example 6
51.66g of USA (from the metallocene catalyst plant, 75.5% dry basis) and 46.86g of Si-Al material SA-1 (from the metallocene catalyst plant, 28.8% silica content, 81.1% dry basis) were taken, and Y-type molecular sieve USY-C (from the catalyst Kaolin Co., ltd., unit cell constant was takenCrystallinity 73.5%) 27.03g, carboxymethyl cellulose B (Shandong Heda Co., ltd.) 1.5g, sesbania powder 3g, and mixing to obtain a mixed powder. 2.1mL of concentrated nitric acid was added to 63mL of water and stirred at room temperature for 5 minutes. Mixing nitric acid solution with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adopting +.>The extruded strips are obtained by a trilobal orifice plate, dried at 110 ℃ for 8 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 3 hours at 590 ℃, the air flow is kept at 40L/h, and the dried strips are taken out after being cooled to room temperature and marked as carrier FC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the tungsten oxide content of 27 wt% and the nickel oxide content of 3wt% in the catalyst, adding 2.50g of ammonium sulfate, adjusting the water quantity, and impregnating the prepared carrier FC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, and then calcined at 420℃for 3 hours, with the air flow rate kept at not less than 15 cubic meters/(kg carrier. Hr) during the calcination, to thereby obtain the catalyst FS.
Example 7
72.00g of USA-2 (from the ziquone catalyst plant, dry basis 75%) and 51.06g of silicon aluminum material SA-2 (from the ziquone catalyst plant, silica content 32.6% and dry basis 80.3%) were taken, and Y-type molecular sieve USY-B (from catalyst Kaolin Co., ltd., unit cell constantCrystallinity 81.4%) 6.00g, carboxymethyl cellulose A (M453, import split charging) 1.75g, sesbania powder 3g, mixingMixing to obtain mixed powder. 0.7mL of concentrated nitric acid was added to 68mL of water and stirred at room temperature for 5 minutes. Mixing nitric acid solution with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adopting +.>The extruded strips are obtained by a trilobal orifice plate, dried at 120 ℃ for 7 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 2 hours at 610 ℃, the air flow is kept at 45L/h, and the dried strips are taken out after being cooled to room temperature and marked as a carrier GC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are all taken from a kaolin catalyst factory) according to the content of tungsten oxide of 24.5 weight percent and the content of nickel oxide of 4.5 weight percent in the catalyst, adding 3.50g of ammonium sulfate, adjusting the water quantity, and impregnating the prepared carrier GC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 430℃for 3 hours, and the air flow rate was maintained at not less than 22.5 cubic meters/(kg carrier. Hr) during calcination, to thereby obtain the catalyst GS.
Comparative example 1
48.65g of SB (from catalyst Kaolin Co., ltd., dry basis 74%) and Si-Al material Siral40 (from catalyst Kaolin Co., ltd., silica content 40.3% and dry basis 79.7%) were taken, 42.66g of Y-type molecular sieve USY-C (from catalyst Kaolin Co., ltd., unit cell constantCrystallinity 73.5%) 35.25g, sesbania powder 3g, and mixing to obtain mixed powder. 1.8mL of concentrated nitric acid was added to 57mL of water and stirred at room temperature for 5 minutes. Mixing nitric acid solution with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adopting +.>The extruded strips are obtained by a trilobal orifice plate, dried at 110 ℃ for 7 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 2.5 hours at 600 ℃, the air flow is kept at 42L/h, and the dried strips are taken out after being cooled to room temperature and are marked as a carrier XC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the tungsten oxide content of 22 weight percent and the nickel oxide content of 6 weight percent in the catalyst, adding 0.00g of ammonium sulfate, adjusting the water quantity, and impregnating the prepared carrier XC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 420℃for 3 hours, and the air flow rate was maintained at not less than 30 cubic meters/(kg carrier. Hour) during calcination, to thereby obtain catalyst XS.
Test example 1
Model number commercially available from Quantachrome IncThe specific surface area and pore volume of the porous supports of examples 1 to 7 and comparative example 1 were determined by the BET method according to the method specified in RIPP 151-90 on a six-station fully automatic specific surface area and pore size distribution meter of 6B, and the specific results are shown in Table 1.
TABLE 1
Test example 2
The once-through process is adopted, and the HVGO is adopted as raw oil. Density (20 ℃ C.) 0.9631g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Sulfur content 17000. Mu.g/g; nitrogen content 3500 mug/g; hydrogen content 10.80%; ni+V<2 μg/g; 3.20% of carbon residue; asphaltenes<0.1%; the distillation range ASTM D-1160, IBP163 ℃; FBP 687 ℃.
Crushing the catalyst into particles with the diameter of 0.5-1.0 mm, loading 150 ml of the catalyst into a 200 ml fixed bed reactor, vulcanizing the catalyst for 28 hours under the conditions of hydrogen partial pressure of 5.0MPa and temperature of 300 ℃ before oil filling, then filling raw oil under the conditions of hydrogen partial pressure of 5.0MPa and temperature of 350 ℃, wherein the hydrogen-oil ratio is 1500 volume/volume, and the liquid hourly space velocity is 5h -1 And sampled after 12 hours and 1000 hours of reaction. The yield of aviation kerosene and the content of heterogeneous hydrocarbon in the hydrogenated oil were determined, and the test results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the catalyst provided by the invention has lower product density and higher hydrogen content in the product by adopting a one-pass process to process heavy oil products. Compared with the comparative example, namely the conventional catalyst preparation method, the catalyst provided by the invention has higher maintenance activity and lower loss rate under a long period (after 240 hours).
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (16)

1. A support for use in the preparation of a hydrogenation catalyst, characterized in that:
the carrier has a bimodal pore structure and contains a non-amorphous mesoporous acid material and 1-30wt% of a Y-type molecular sieve, wherein the non-amorphous mesoporous acid material is a silicon-aluminum composite oxide;
in the bimodal pore structure, the pore diameter of a macropore which can be few pores is in the range of 300-750 nm, the pore diameter of a micropore which can be few pores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropore which can be few pores to the pore diameter of the micropore which can be few pores is 45-95;
the hole concentration value of the small holes is not lower than 0.5;
the ratio of the pore volume of the large pore to the pore volume of the small pore is 3-10, the pore volume of the large pore is the cumulative pore volume of pores with the pore diameter within 50-150% of the pore diameter of the small pore, and the pore volume of the small pore is the cumulative pore volume of pores with the pore diameter within 50-150% of the pore diameter of the small pore; the pore volume of the macropores accounts for 15-20% of the total pore volume of the carrier.
2. The carrier according to claim 1, wherein in the carrier, the macropore has a switchable pore diameter in a range of 450 to 700nm, and the macropore has a switchable pore diameter in a range of 5 to 9 nm.
3. The carrier of claim 1, wherein the pores have a pore concentration value of not less than 0.75.
4. A process for preparing the vector of any one of claims 1 to 3, comprising:
s1, mixing pseudo-boehmite, amorphous silicon aluminum oxide, a Y-type molecular sieve, carboxymethyl cellulose and sesbania powder to obtain mixed powder; the weight ratio of the pseudo-thin aluminum terrazzo to the amorphous silicon aluminum oxide to the Y-type molecular sieve to the carboxymethyl cellulose to the sesbania powder is 10-65: 25-80: 1-30: 0.1 to 3.0: 2.5-3.5;
s2, mixing the mixed powder with a nitric acid solution, kneading and extruding to obtain an extruded strip;
s3, carrying out first drying and first roasting on the extruded strip.
5. The preparation method of claim 4, wherein in the step S1, the weight ratio of the pseudo-boehmite, the amorphous silica-alumina, the Y-type molecular sieve, the carboxymethyl cellulose and the sesbania powder is 15-60: 30-75: 2-25: 0.2-2.8: 2.8-3.2;
in the step S2, the consumption of the nitric acid solution is 50-130 mL relative to each 100g of the mixed powder.
6. The process according to claim 4 or 5, wherein,
SiO in the pseudo-thin alexandrite 2 Less than 0.1 to wt percent, fe 2 O 3 Less than 0.01 and wt percent of Na 2 The content of O is less than 0.15 and wt percent, the content of water is less than 3 and wt percent, and the ignition loss is 32-38wt%; the pore volume of the pseudo-thin aluminum water stone is 0.60-1.1mL/g, and the specific surface is 220-310m 2 /g；
SiO in the amorphous silicon aluminum oxide 2 Is 15-55wt%, al 2 O 3 The content of (2) is 45-85wt%, and the bulk density is 250-450 g/L;
the unit cell constant of the Y-type molecular sieve is 2.425-2.460 nm, and the crystallinity is 50-90%; specific surface area of 550-750 m 2 /g; the pore volume is 0.32-0.56 mL/g, and the sodium oxide content is 0.05-0.30wt%;
the sodium content in the 2% aqueous solution of the carboxymethyl cellulose is less than 2.0 and wt%;
the mass concentration of the nitric acid solution is 0.3-2.5%.
7. The production method according to claim 4 or 5, wherein, in step S2, the conditions of mixing include: the temperature is 10-40 ℃ and the time is 1-10 minutes;
in step S3, the first drying conditions include: the temperature is 100-130 ℃ and the time is 3-20 hours; the conditions of the first firing include: the temperature is 400-600 ℃, the time is 2-10 hours, and the air flow is 20-50L/h.
8. A hydrogenation catalyst comprising the support of any one of claims 1 to 3 and an active metal component.
9. The hydrogenation catalyst of claim 8, wherein the active metal component is selected from the group consisting of group VIII and/or group VIB metal elements;
the VIII metal element is cobalt and/or nickel, and the VIB metal element is molybdenum and/or tungsten.
10. The hydrogenation catalyst according to claim 9, wherein the group VIB metal content is 20-30 wt.% and the group VIII metal content is 1.5-8.5 wt.% based on the total catalyst and calculated as oxide.
11. A method for preparing a hydrogenation catalyst, comprising:
SS1, impregnating the support according to any one of claims 1 to 3 with an aqueous solution containing a hydrogenation-active component compound to obtain an impregnated support;
SS2, subjecting the impregnated support to a second drying and a second calcination.
12. The production process according to claim 11, wherein the hydrogenation-active component compound comprises a group VIII metal-containing compound and/or a group VIB metal-containing compound;
the compound containing the VIII group metal is at least one of nitrate, acetate, carbonate, chloride and complex of nickel and cobalt; the group VIB metal-containing compound comprises at least one of molybdic acid, paramolybdic acid, molybdate, para-molybdate, tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate, and ethyl metatungstic acid.
13. The production method according to claim 11, wherein the aqueous solution containing the hydrogenation-active component compound contains ammonium sulfate.
14. The preparation method according to claim 11, wherein,
in step SS1, the conditions of the impregnation include: the soaking temperature is 5-150 ℃ and the soaking time is 0.5-12 hours;
in step SS2, the conditions of the second drying process include: the drying temperature is 80-350 ℃; the drying time is 0.5-24 hours; the conditions of the second firing include: the roasting temperature is 360-700 ℃; the roasting time is 0.2-12 hours.
15. The preparation method according to claim 11, wherein,
in step SS2, the conditions of the second drying process include: the drying temperature is 100-300 ℃; the drying time is 1-12 hours; the conditions of the second firing include: the roasting temperature is 400-650 ℃; the roasting time is 1-10 hours.
16. A method for producing low BMCI value tail oil and high yield aviation kerosene by hydro-upgrading heavy distillate oil, characterized in that the heavy distillate oil and hydrogen are contacted with the hydrogenation catalyst of any one of claims 8-10 under hydrogenation conditions.
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