CN114433245B - Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate - Google Patents

Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate Download PDF

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CN114433245B
CN114433245B CN202011193833.6A CN202011193833A CN114433245B CN 114433245 B CN114433245 B CN 114433245B CN 202011193833 A CN202011193833 A CN 202011193833A CN 114433245 B CN114433245 B CN 114433245B
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pore
catalyst
carrier
hydrogenation
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CN114433245A (en
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董松涛
杨清河
杨平
赵广乐
渠红亮
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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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    • B01J35/615—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/14—Silica and magnesia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J35/635—
    • B01J35/638—
    • B01J35/69—
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • 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

Abstract

The invention provides a carrier for preparing a hydrogenation catalyst, the hydrogenation catalyst and a hydrogenation modification method of heavy distillate. The carrier has a bimodal pore structure; in the bimodal pore structure, the pore diameter of the macropores is in the range of 200-800 nm, the pore diameter of the micropores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropores to the pore diameter of the micropores is 50-100; the ratio of the pore volume of the large pore to the pore volume of the small pore is 3-10. The hydrogenation catalyst comprises the carrier and an active metal component. The catalyst provided by the invention can be used for processing heavy distillate oil to obtain a product with lower density and higher hydrogen content.

Description

Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate
Technical Field
The invention relates to the field of catalysts or carriers, in particular to a catalyst carrier, a hydrogenation catalyst and a hydrogenation modification method of heavy distillate oil.
Background
The hydrocracking technology is one of the classical means for hydroconversion of heavy distillate oil and has the characteristics of high product quality, long service period, flexible operation and the like. The method is used for processing conventional oil products such as VGO, LCO and the like, and has the advantages which are not possessed by other technologies. However, when the catalyst is used for processing heavy fractions, particularly heavy fractions with a dry point of more than 600 ℃, the catalyst performance is often unstable, and the service life is long.
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 bifunctional catalyst having both cracking activity and hydrogenation activity, i.e., containing both an acidic component and a hydrogenation active component, the acidity of which is mainly provided by the refractory inorganic oxide and/or various zeolites constituting the support; the hydrogenation-active component is generally selected from the group consisting of metals of groups VIB and VIII of the periodic table of the elements, metal oxides and/or metal sulfides. In order to meet the different requirements of hydrocracking products, the acidic components and hydrogenation active components 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. Compared with molecular sieve, the preparation method of amorphous silica-alumina is simple, low in cost, has larger pore diameter, larger silica-alumina ratio adjusting range and lower acid density, and is especially suitable for treating macromolecular raw materials such as heavy oil, residual oil and the like. Amorphous silica alumina is an acidic support for many industrial amorphous catalysts and is also an important component of many molecular sieve catalysts, but a common 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. The molecular sieve or mesoporous material is selected, and even the solid super acid can adjust the property of the acidic component in a larger range, so that the acidic function of the catalyst is optimized. 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.
For example: chinese patent CN104437542B provides a catalyst for preparing distillate oil from synthesis gas, its preparation and application, and the pore volume of pores with diameter of 10-30 nm is controlled to be 55-80% of total pore volume, and the pore volume of pores with diameter of 300-500 nm is controlled to be 10-35% of total pore volume. The catalyst provided by the patent has better Fischer-Tropsch synthesis reaction performance.
Chinese patent CN104338538A provides a heavy oil hydrodemetallization catalyst and preparation and application thereof, wherein the pore volume of pores with diameters of 5-20nm is controlled to be 30-60% of the total pore volume, and the pore volume of pores with diameters of 100-300nm is controlled to be 15-45% of the total pore volume. Compared with the prior art, the catalyst provided by the invention has better hydrodeasphaltene and demetallization performance when being used for hydrotreating residual oil.
Chinese patent CN1129606a bimodal pore distribution hydrocarbon conversion catalyst and method of making same. The invention is said to be due to the addition of Al (OH) 3, macroporous pore formers and carboxymethyl cellulose. Therefore, the catalyst provided by the invention can save 10% of catalyst under the same industrial conditions.
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. The method is used for processing oil products which are heavier than the conventional VGO, but lighter than residual oil, and have too many macropores and less necessity. Thus, there is a need for a suitable hydrogenation catalyst to process heavy wax oil components that are heavier than VGO.
Disclosure of Invention
The invention aims to provide a hydro-upgrading method suitable for heavy distillate oil.
In order to achieve the above object, a first aspect of the present invention provides a support for preparing a hydrogenation catalyst, the support having a bimodal pore structure; in the bimodal pore structure, the pore diameter of the macropores is in the range of 200-800 nm, the pore diameter of the micropores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropores to the pore diameter of the micropores is 50-100; 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 and carboxymethyl cellulose 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 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.
In a fifth aspect, the present invention provides a method for hydro-upgrading a 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 a carrier and an active metal component, and the catalyst provided by the invention is adopted to process heavy distillate oil, so that the obtained product has lower density and higher hydrogen content.
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.
The first aspect of the present invention provides a support for preparing a hydrogenation catalyst, the support having a bimodal pore structure; in the bimodal pore structure, the pore diameter of the macropores is in the range of 200-800 nm, the pore diameter of the micropores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropores to the pore diameter of the micropores is 50-100; 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.
Wherein, the bimodal pore in the invention refers to the existence of two obvious peaks on a pore distribution curve of mercury intrusion or BET, wherein the position of the fixed point of the peak becomes accessible pore diameter. 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 coverage of 50% up and down of the pore diameter means that the pore volume in the range of the pore diameter is accumulated in the whole coverage of 5-15 nm of a given accessible pore diameter, such as an accessible pore diameter of 10 nm.
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 is the pore diameter corresponding to the maximum value of dV/dr in the distribution curve of the derivative of specific pore volume to pore diameter (i.e., dV/dr) with pore diameter obtained when the pore structure of the sample is measured by the BET method.
As a preferred embodiment of the present invention, the macropores have a pore diameter of 450 to 700nm and the micropores have a pore diameter of 5 to 9 nm; the pore volume of the macropores accounts 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 invention, the support may be a non-amorphous mesoporous acidic material; 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 producing a carrier for a hydrogenation catalyst, the process comprising:
s1, mixing pseudo-boehmite, amorphous silicon-aluminum oxide and carboxymethyl cellulose 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 a second aspect of the present invention, in step S1, the weight ratio of the pseudo boehmite, the amorphous silica alumina, and the carboxymethyl cellulose may be 5 to 70:30-95:0.05-5.0; preferably 10-60:40-90:0.1-3.0; in step S2, the nitric acid solution may be used in an amount of 75 to 150mL per 100g of the mixed powder on a dry basis.
According to a second aspect of the invention, the pseudoboehmite may be characterized in that it comprises: 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%; the pore volume of the pseudo-boehmite 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 (3) is 15-55wt%, al 2 O 3 The content of the catalyst is 45-85 wt% and the bulk density is 250-450 g/L; as a preferred embodiment of the present invention, the sodium content of the 2% aqueous solution of carboxymethyl cellulose is less than 2.0wt%; the mass concentration of the nitric acid solution is 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.
In a third aspect the present invention provides a hydrogenation catalyst comprising the support and an active metal component as described above.
According to a third aspect of the invention, the active metal component may be selected from 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.
Preferably, the group VIB metal content, calculated as oxide and based on the total catalyst, may be 20 to 30 wt.%, and the group VIII metal content may be 1.5 to 8.5 wt.%.
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 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.
In a fifth aspect, the present invention provides a method for hydro-upgrading a 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. The dry basis in the examples and comparative examples was determined by calcining the samples at 600 ℃ for 4 hours.
Example 1
35.7g of CL-B (from catalyst Kaolin Co., ltd., dry basis 64.5%) and 96.6g of Si-Al material Siral28M (from SASOL production, silica content 27.7% and dry basis 79.7%) and 0.30g of carboxymethyl cellulose A (M450, inlet split charging) were taken and mixed to obtain a mixed powder. 1.0mL of concentrated nitric acid was added to 128mL 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 adoptingThe 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 (taken from a kaolin catalyst factory) according to the content of tungsten oxide in the catalyst being 23.0 wt% and the content of nickel oxide being 5.5 wt%, 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
Taking CL-B (taken from catalysis)51.2g of Kaolin, 64.5% dry basis, 84.1g of silica-alumina material Siral28m (obtained from SASOL production, silica content 27.7% dry basis 79.7%), and 0.70g of carboxymethyl cellulose B (Shandong Heda Co., ltd.) were mixed to obtain a mixed powder. 2.1mL of concentrated nitric acid was added to 112mL 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 adoptingThe 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 (taken from a kaolin catalyst factory) according to the tungsten oxide content of 25.0 wt% and the nickel oxide content of 7.0 wt% in the catalyst, adjusting the water content, 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
24.3g of CL-A (from catalyst Kaolin Co., ltd., dry basis: 74%) and 104.8g of silicon aluminum material SA-2 (from zipcocene catalyst Co., silica content: 28.8% and dry basis: 81.1%) were taken, and 1.10g of carboxymethyl cellulose A (M451, split charging at inlet) were mixed to obtain a mixed powder. 0.7mL of concentrated nitric acid was added to 142mL 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 adoptingThe 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 (taken from a kaolin catalyst factory) according to the content of tungsten oxide in the catalyst of 26.0 weight percent and the content of nickel oxide of 4.0 weight percent, adjusting the water quantity, and impregnating the prepared carrier CC by adopting a pore saturation method. The impregnated porous support 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 support. Hr) during the calcination, to thereby obtain the catalyst CS.
Example 4
58.1g of CL-A (from catalyst Kaolin Co., ltd., dry basis 74%) and 74.7g of silica-alumina material SA-2 (from zipcocene catalyst Co., silica content 32.6%, dry basis 80.3%) were taken, and 1.50g of carboxymethyl cellulose B (Shandong Heda Co., ltd.) were mixed to obtain a mixed powder. 1.8mL 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 adoptingThe extruded strips are obtained by drying the extruded strips at 130 ℃ for 4 hours, the dried strips are taken and put into a roasting furnace, the dried strips are treated at 560 ℃ for 3 hours, the air flow is kept at 35L/h, the temperature is reduced to room temperature, and the dried strips are taken out and marked as carrier DC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (taken from a kaolin catalyst factory) according to the content of tungsten oxide in the catalyst being 24.0 wt% and the content of nickel oxide being 5.0 wt%, 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
37.1g of USA (from the metallocene catalyst plant, 75.5% dry basis) and 95.4g of silicon-aluminum material SA-3 (from the metallocene catalyst plant, 39.7% silicon oxide content, 78.6% dry basis) are taken, 1.90g of carboxymethyl cellulose A (M452, split charging in inlet) are taken and mixed to obtain mixed powder. 0.3mL of concentrated nitric acid was added to 125mL of water and stirred at room temperature for 5 minutes. Mixing nitric acid solution with the mixed powder, and extruding into stripsRepeatedly kneading for 3 times by adoptingThe 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 (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, 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
50.3g of USA (from the ziquone catalyst plant, 75.5% on dry basis) and 80.1g of silicon aluminum material SA-1 (from the ziquone catalyst plant, 28.8% on silica, 81.1% on dry basis) were taken, and 2.30g of carboxymethyl cellulose B (Shandong Heda Co., ltd.) were mixed to obtain a mixed powder. 1.4mL of concentrated nitric acid was added to 108mL 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 adoptingThe 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, a mixed aqueous solution of nickel nitrate and ammonium metatungstate (obtained from a kaolin catalyst factory) is prepared according to the tungsten oxide content of 27.0 wt% and the nickel oxide content of 3.0 wt% in the catalyst, the water content is adjusted, and the prepared carrier FC is impregnated by 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
70.7g of USA-2 (from the self-aligned catalyst plant, dry basis 75%) and 62.3g of silicon-aluminum material SA-2 (from the self-aligned catalyst plant, silicon oxide content 32.6% and dry basis 80.3%) are taken, 2.70g of carboxymethyl cellulose A (M453, inlet split charging) are taken and mixed to obtain mixed powder. 2.4mL of concentrated nitric acid was added to 83mL 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 adoptingThe 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, a mixed aqueous solution of nickel nitrate and ammonium metatungstate (obtained from a kaolin catalyst factory) is prepared according to the content of tungsten oxide in the catalyst of 24.5 weight percent and the content of nickel oxide of 4.5 weight percent, the water quantity is adjusted, and a pore saturation method is adopted to impregnate the prepared carrier GC. 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
46.5g of CL-B (from catalyst Kaolin Co., ltd., dry basis 64.5%) and 87.2g of silica-alumina material SA-2 (from zipcocene catalyst Co., silica content 32.6% and dry basis 80.3%) were taken and mixed to obtain a mixed powder. 2.8mL of concentrated nitric acid was added to 117mL 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 adoptingThe trilobal orifice plate is extruded to obtain the dried strips, the extruded strips are dried at 120 ℃ for 6 hours to obtain the dried strips, the dried strips are taken and put into a roasting furnace to be treated at 600 ℃ for 3 hours, the air flow is kept at 42L/h, and the dried strips are cooled to room temperature and taken out and are marked as a carrier XC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (taken from a kaolin catalyst factory) according to the content of tungsten oxide in the catalyst of 26.0 weight percent and the content of nickel oxide of 2.8 weight percent, adjusting the water quantity, and impregnating the prepared carrier XC by adopting a pore saturation method. The impregnated carrier was dried at 120℃for 6 hours, followed by calcination at 430℃for 3 hours, and the air flow rate was maintained at not less than 14 cubic meters/(kg carrier. Hr) 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 and pore size distribution determinator of 6B. The test 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 ℃): 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 150ml 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 1500 volume/volume5h -1 And sampled after 12 hours and 1000 hours of reaction. The yield of aviation kerosene and the content of isomerised hydrocarbons in the hydrogenated oil were determined and the specific results are shown in Table 2.
TABLE 2
Examples 48h catalyst Activity/. Degree.C 240h catalyst Activity/. Degree.C Loss of Activity/. Degree.C Product density Product hydrogen content/%
AS 400.8 402.4 1.6 0.8950 12.68
BS 401.6 403.0 1.4 0.8951 12.68
CS 399.9 401.3 1.4 0.8967 12.64
DS 401.3 402.7 1.3 0.8955 12.67
ES 398.4 400.1 1.8 0.8967 12.64
FS 401.6 404.7 3.1 0.8976 12.62
GS 402.3 405.3 3.0 0.8959 12.66
XS 400.4 410.6 10.2 0.8972 12.63
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 (17)

1. A support for use in the preparation of a hydrogenation catalyst, characterized in that:
the carrier has a bimodal pore structure;
the carrier is a non-amorphous mesoporous acid material; the non-amorphous mesoporous acid material is 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 450-700 nm, the pore diameter of a micropore which can be few pores is in the range of 5-9 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 50-100;
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; the pore concentration value of the small pores is not lower than 0.5.
2. The carrier of claim 1, wherein the pores have a pore concentration value of not less than 0.75.
3. A method for producing the carrier for producing a hydrogenation catalyst according to claim 1 or 2, characterized by comprising:
s1, mixing pseudo-boehmite, amorphous silicon-aluminum oxide and carboxymethyl cellulose 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.
4. A production method according to claim 3, wherein in step S1, the weight ratio of the pseudo-boehmite, the amorphous silica-alumina oxide and the carboxymethyl cellulose is 5 to 70:30-95:0.05-5.0;
in step S2, the amount of the nitric acid solution is 75-150mL per 100g of the mixed powder.
5. The preparation method according to claim 3, wherein the weight ratio of the pseudo-boehmite, the amorphous silica-alumina and the carboxymethyl cellulose is 10 to 60:40-90:0.1-3.0.
6. The method according to any one of claims 3 to 5, wherein,
SiO in the pseudo-boehmite 2 The content of (C) is less than 0.1wt%, fe 2 O 3 The content of (2) is 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%; the pore volume of the pseudo-boehmite is 0.60-1.1mL/g, and the specific surface is 220-310m 2 /g；
SiO in the amorphous silicon aluminum oxide 2 Is 15-55 wt%, al 2 O 3 The content of (2) is 45-85 wt%, and the bulk density is 250-450 g/L;
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 preparation method according to any one of claims 3 to 5, wherein in step S2, the mixing conditions 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 claim 1 or 2 and an active metal component.
9. The hydrogenation catalyst of claim 8 wherein the catalyst is selected from the group consisting of,
the active metal component is selected from metal elements of the VIII group and/or the VIB group.
10. The hydrogenation catalyst according to claim 9, wherein the group VIII metal element is cobalt and/or nickel and the group VIB metal element is molybdenum and/or tungsten.
11. 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.
12. A method for preparing a hydrogenation catalyst, comprising:
SS1, impregnating the support of claim 1 or 2 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.
13. The preparation method according to claim 12, wherein,
the hydrogenation active component compound comprises a compound containing VIII group metal and/or a compound containing VIB group metal.
14. The production method according to claim 13, wherein the group VIII metal-containing compound 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.
15. The preparation method according to claim 12, 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.
16. The production method according to claim 15, wherein the conditions of the second drying treatment 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.
17. A process for the hydro-upgrading of a heavy distillate, characterized in that the heavy distillate and hydrogen are contacted with a hydrogenation catalyst according to any one of claims 8-11 under hydrogenation conditions.
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