CN110064403B - Preparation method of hydrotreating catalyst with denitrification activity - Google Patents
Preparation method of hydrotreating catalyst with denitrification activity Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a preparation method of a hydrotreating catalyst with denitrification activity, which comprises the following steps: step 1, preparing a porous carrier based on alumina or a phosphorus-containing alumina material; step 2, impregnating the porous carrier with a metal I solution, curing, drying and roasting to obtain a catalyst precursor, wherein the metal I solution is a NiMoP solution containing Ni, Mo and P elements or a CoMoP solution containing Co, Mo and P elements; step 3, dipping the catalyst precursor into a II-type metal solution containing an organic auxiliary agent, and then curing and drying the catalyst precursor without roasting to obtain a final catalyst; the II-type metal solution is a NiMoP solution containing Ni, Mo and P elements or a CoMoP solution containing Co, Mo and P elements, and the I-type metal solution and the II-type metal solution are not the NiMoP solution or the CoMoP solution at the same time. The catalyst prepared by the method has high denitrification activity.
Description
Technical Field
The invention relates to a preparation method of a high-activity hydrotreating catalyst, in particular to a NiCoMo high-activity denitrification catalyst and a preparation method and application thereof.
Background
The existence of impurities such as sulfur, nitrogen, metal and the like in the distillate oil can not only influence the oxidation stability of the finished oil, but also discharge SO2、NO2And the like. The removal of impurities from the distillate by hydrotreating is a very necessary measure. The distillate oil hydrotreating target is to convert organic sulfur in the raw material into hydrogen sulfide and organic nitrogen into ammonia gas. The fraction oil hydrogenation treatment is a process of contacting fraction oil and hydrogen with a catalyst under a certain temperature and pressure condition to remove impurities and saturate aromatic hydrocarbon. Thus, the preparation method of the hydrotreating catalyst was developed to obtain high activityThe catalyst (c) is important.
At present, the methods for desulfurization, denitrification and dearomatization of diesel oil fractions generally adopt a two-stage method, namely, a first stage of hydrodesulfurization and denitrification, and a second stage of hydrogenation dearomatization. Conventional hydrodesulfurization and denitrogenation catalysts generally comprise a carrier and a group VIB and/or group VIII active metal component loaded on the carrier, wherein the most common group VIB metals are molybdenum and tungsten, and the group VIII metals are nickel and cobalt, and the catalysts also often contain auxiliary agents such as phosphorus, boron and the like. The catalyst is generally prepared by supporting the active component on a support, for example by impregnation, and then converting it to the oxidized state by drying and calcination at high temperature. The catalyst is presulfided to convert it to the sulfided state prior to use in hydroprocessing. Therefore, a large amount of energy is wasted, the cost of the catalyst is increased, and the catalyst performance is reduced because some non-ideal phases with low or even no activity are formed by high-temperature roasting after the active metal is loaded.
It is reported that the organic compound is added into the metal impregnation liquid and impregnated on the porous carrier, so that more high-activity II-type active phase can be generated, and simultaneously, the activity loss caused by metal aggregation in the high-temperature vulcanization process of the catalyst can be prevented, thereby improving the activity of the hydrotreating catalyst. Many patents disclose the use of various organic compounds, such as oxygen-containing organic compound polyols or etherates thereof (WO96/41848, US3954673, US 4012340).
Patent JP 04166231 discloses a method for preparing a hydrotreating catalyst by impregnating a porous support with a metal solution, drying the impregnated support at a temperature of not higher than 200 ℃, and subjecting the dried support to a drying step after contacting the support with a polyol.
EP 0601722 discloses a method for preparing a catalyst, characterized in that a porous alumina carrier is impregnated with an aqueous metal solution containing a glycol, and the impregnated carrier is subjected to a primary drying step without being subjected to a calcination process to prepare a finished catalyst.
US 6218333 discloses a method of preparing a hydroprocessing catalyst by combining a porous support with an active metal component to form a catalyst precursor having volatiles. The catalyst precursor is treated with a sulfur-containing compound, and volatiles are released from the catalyst precursor under dry conditions. However, these improvements are not sufficient to meet the increasingly stringent fuel requirements of refineries.
The high activity of the hydrotreating catalyst can make the hydrotreating process conditions moderate, such as low reaction temperature, or obtain products with better quality under the same conditions. Therefore, how to develop a highly active hydrotreating catalyst is an object of constant search by those skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a hydrotreating catalyst with denitrification activity.
In order to achieve the above object, the present invention provides a method for preparing a hydrotreating catalyst having denitrification activity, comprising the steps of:
step 1, preparing a porous carrier based on alumina or a phosphorus-containing alumina material;
step 2, impregnating the porous carrier with a metal I solution, curing, drying and roasting to obtain a catalyst precursor, wherein the metal I solution is a NiMoP solution containing Ni, Mo and P elements or a CoMoP solution containing Co, Mo and P elements;
step 3, dipping the catalyst precursor into a II-type metal solution containing an organic auxiliary agent, and then curing and drying the catalyst precursor without roasting to obtain a final catalyst; the II-type metal solution is a NiMoP solution containing Ni, Mo and P elements or a CoMoP solution containing Co, Mo and P elements, and the I-type metal solution and the II-type metal solution are not the NiMoP solution or the CoMoP solution at the same time.
In the preparation method of the hydrotreating catalyst with denitrification activity, the organic auxiliary agent in the step 2 contains alcohols and/or organic acids.
The preparation method of the hydrotreating catalyst with denitrification activity, provided by the invention, comprises the following steps of (1) using the organic auxiliary agent in step 3: the organic auxiliary agent is contained in an amount of 0.01 to 3 mol per mol of the active metal based on the metal II solution.
After the II type catalyst is introduced with the organic auxiliary agent, the generated metal particles have small size, so the activity is high. However, if the type II catalyst is used alone, the interaction between the metal and the carrier is weak, and the stability of the catalyst cannot be ensured, resulting in poor denitrification activity.
In the preparation method of the hydrotreating catalyst with denitrification activity of the present invention, the drying in step 3 is a drying method commonly used in the art, such as vacuum drying or atmospheric drying, and is not particularly limited, and may be one-time or multi-step drying.
According to the preparation method of the hydrotreating catalyst with denitrification activity, the drying temperature in the step 3 is lower than 260 ℃.
The preparation method of the hydrotreating catalyst with denitrification activity has the drying temperature of 100-260 ℃ in the step 3
According to the preparation method of the hydrotreating catalyst with denitrification activity, the alcohol organic auxiliary agent is polyethylene glycol.
According to the preparation method of the hydrotreating catalyst with denitrification activity, the organic acid organic auxiliary agent is citric acid.
According to the preparation method of the hydrotreating catalyst with denitrification activity, the ratio of the I-type active sites to the II-type active sites in the catalyst is within 0.1-0.5.
The preparation method of the hydrotreating catalyst with denitrification activity, disclosed by the invention, has the advantages that in the step 2, the drying temperature is 100-300 ℃, and the roasting temperature is 400-550 ℃.
The invention has the beneficial effects that:
a hydrotreating catalyst having a combination of different types of metals and different types of active sites and having a high denitrification activity is provided.
Drawings
FIG. 1 is a flow chart of a process for producing a catalyst in example 1 of the present invention;
FIG. 2 is a flow chart of the production process of the catalyst in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to specific examples so as to facilitate understanding of the objects and technical contents of the present invention, and the embodiments are only for illustration and are not intended to limit the present invention.
A preparation method of a hydrotreating catalyst with denitrification activity comprises the following steps:
step 1, preparing a porous carrier based on alumina or a phosphorus-containing alumina material;
step 2, impregnating the porous carrier with a metal I solution, curing, drying and roasting to obtain a catalyst precursor, wherein the metal I solution is a NiMoP solution containing Ni, Mo and P elements or a CoMoP solution containing Co, Mo and P elements;
step 3, dipping the catalyst precursor into a II-type metal solution containing an organic auxiliary agent, and then curing and drying the catalyst precursor without roasting to obtain a final catalyst; the II-type metal solution is a NiMoP solution containing Ni, Mo and P elements or a CoMoP solution containing Co, Mo and P elements, and the I-type metal solution and the II-type metal solution are not the NiMoP solution or the CoMoP solution at the same time.
In the preparation method of the hydrotreating catalyst with denitrification activity, the organic auxiliary agent in the step 2 contains alcohols and/or organic acids.
The preparation method of the hydrotreating catalyst with denitrification activity, provided by the invention, comprises the following steps of (1) using the organic auxiliary agent in step 3: the organic auxiliary agent is contained in an amount of 0.01 to 3 mol per mol of the active metal based on the metal II solution.
In the preparation method of the hydrotreating catalyst with denitrification activity of the present invention, the drying in step 3 is a drying method commonly used in the art, such as vacuum drying or atmospheric drying, and is not particularly limited, and may be one-time or multi-step drying.
According to the preparation method of the hydrotreating catalyst with denitrification activity, the drying temperature in the step 3 is lower than 260 ℃.
The preparation method of the hydrotreating catalyst with denitrification activity has the drying temperature of 100-260 ℃ in the step 3
According to the preparation method of the hydrotreating catalyst with denitrification activity, the alcohol organic auxiliary agent is polyethylene glycol.
According to the preparation method of the hydrotreating catalyst with denitrification activity, the organic acid organic auxiliary agent is citric acid.
According to the preparation method of the hydrotreating catalyst with denitrification activity, the ratio of the I-type active sites to the II-type active sites in the catalyst is within 0.1-0.5.
The preparation method of the hydrotreating catalyst with denitrification activity, disclosed by the invention, has the advantages that in the step 2, the drying temperature is 100-300 ℃, and the roasting temperature is 400-550 ℃.
EXAMPLE 1 preparation of Ni/CoMo catalyst type I/II C1 (according to the invention)
Step 1, extruding, drying and roasting pseudo-boehmite to prepare clover-shaped A12O3A carrier;
step 2, molybdenum trioxide (24g) and basic nickel carbonate (5g) were thermally dissolved in a hot phosphoric acid solution (8g) having a concentration of 85% to prepare a NiMoP solution. Adding NiMoP solution into 70g of the carrier, curing the extrudate at room temperature for 6 hours after impregnation, drying the extrudate at 120 ℃ overnight, and roasting the extrudate at 450 ℃ for 3 hours to obtain a type I catalyst precursor;
and step 3, thermally dissolving molybdenum trioxide (24g) and cobalt hydroxide (6g) in a hot phosphoric acid solution (8g) with the concentration of 85% to prepare a CoMoP solution. The catalyst precursor was impregnated with a mixed solution of CoMoP-CA (citric acid) (citric acid/Mo ═ 0.1, molar ratio), and then aged at room temperature for 6 hours and dried at 100 ℃ for 6 hours to obtain Ni/CoMo type I/II catalyst C1.
EXAMPLE 2 preparation of Co/NiMo catalyst type I/II C2 (according to the invention)
Step 1, extruding, drying and roasting pseudo-boehmite to prepare clover-shaped A12O3A carrier;
step 2, molybdenum trioxide (24g) and cobalt hydroxide (6g) were thermally dissolved in a hot phosphoric acid solution (8g) having a concentration of 85% to prepare a CoMoP solution. The CoMoP mixed solution was added to 70g of the above-mentioned support, and after impregnation the extrudate was aged at room temperature for 6 hours, dried at 100 ℃ and calcined at 450 ℃ for 3 hours to obtain a type I catalyst precursor.
And 3, thermally dissolving molybdenum trioxide (24g) and basic nickel carbonate (5g) in a hot phosphoric acid solution (8g) with the concentration of 85% to prepare a NiMoP solution. The catalyst precursor was impregnated with a mixed solution of NiMoP-CA (citric acid) (citric acid/Mo ═ 0.1, molar ratio), and then aged at room temperature for 6 hours and dried at 260 ℃ for 6 hours, to obtain a type I/II Co/NiMo catalyst C2.
EXAMPLE 3 preparation of Ni/CoMo catalyst type I/II C3 (according to the invention)
Step 1, extruding, drying and roasting pseudo-boehmite to prepare clover-shaped A12O3A carrier;
step 2, molybdenum trioxide (24g) and basic nickel carbonate (5g) were thermally dissolved in a hot phosphoric acid solution (8g) having a concentration of 85% to prepare a NiMoP solution. Adding NiMoP solution into 70g of the carrier, curing the extrudate at room temperature for 6 hours after impregnation, drying overnight at 200 ℃, and roasting at 450 ℃ for 3 hours to obtain a type I catalyst precursor;
and step 3, thermally dissolving molybdenum trioxide (24g) and cobalt hydroxide (6g) in a hot phosphoric acid solution (8g) with the concentration of 85% to prepare a CoMoP solution. After the catalyst precursor was impregnated with a CoMoP-PEG (polyethylene glycol, molecular weight 600, polyethylene glycol/Mo ═ 0.01, molar ratio) mixed solution, it was aged at room temperature for 6 hours, and dried at 200 ℃ for 6 hours to obtain Ni/CoMo type I/II catalyst C3.
EXAMPLE 4 preparation of Co/NiMo catalyst type I/II C4 (according to the invention)
Step 1, extruding, drying and roasting pseudo-boehmite to prepare clover-shaped A12O3A carrier;
step 2, molybdenum trioxide (24g) and cobalt hydroxide (6g) were thermally dissolved in a hot phosphoric acid solution (8g) having a concentration of 85% to prepare a CoMoP solution. And adding the CoMoP mixed solution into 70g of the carrier, curing the extrudate at room temperature for 6 hours after soaking, drying at 120 ℃, and roasting at 400-550 ℃ for 4 hours to obtain the catalyst precursor.
And 3, thermally dissolving molybdenum trioxide (24g) and basic nickel carbonate (5g) in a hot phosphoric acid solution (8g) with the concentration of 85% to prepare a NiMoP solution. The catalyst precursor was impregnated with a mixed solution of NiMoP-CA-PEG (polyethylene glycol, molecular weight 600, polyethylene glycol/Mo ═ 0.01, molar ratio), then aged at room temperature for 6 hours, and dried at 100-260 ℃ for 6 hours to obtain I/II type Co/NiMo catalyst C4.
EXAMPLE 5 preparation of Co/NiMo catalyst type I/II C5 (according to the invention)
Step 1, extruding, drying and roasting pseudo-boehmite to prepare clover-shaped A12O3A carrier;
step 2, molybdenum trioxide (24g) and cobalt hydroxide (6g) were thermally dissolved in a hot phosphoric acid solution (8g) having a concentration of 85% to prepare a CoMoP solution. And adding the CoMoP mixed solution into 70g of the carrier, curing the extrudate at room temperature for 6 hours after soaking, drying at 120 ℃, and roasting at 400-550 ℃ for 4 hours to obtain the catalyst precursor.
And 3, thermally dissolving molybdenum trioxide (24g) and basic nickel carbonate (5g) in a hot phosphoric acid solution (8g) with the concentration of 85% to prepare a NiMoP solution. The catalyst precursor was impregnated with a mixed solution of NiMoP-CA-PEG (polyethylene glycol, molecular weight 600, polyethylene glycol/Mo ═ 0.01, molar ratio), then aged at room temperature for 6 hours, and dried at 100-260 ℃ for 6 hours to obtain I/II type Co/NiMo catalyst C5.
Comparative example 1 preparation of type I NiCoMo catalyst C1 (not according to the invention)
Step 1, extruding, drying and roasting pseudo-boehmite to prepare clover-shaped A12O3And (3) a carrier.
Step 2, molybdenum trioxide (24g) and basic nickel carbonate (5g) were thermally dissolved in a hot phosphoric acid solution (8g) having a concentration of 85% to prepare a NiMoP solution. The NiMoP solution was added to 70g of the above support, and after impregnation the extrudates were allowed to age at room temperature for 6 hours and dried at 120 ℃ overnight.
And step 3, thermally dissolving molybdenum trioxide (24g) and cobalt hydroxide (6g) in a hot phosphoric acid solution (8g) with the concentration of 85% to prepare a CoMoP solution. After the catalyst precursor was impregnated with the CoMoP solution, it was aged at room temperature for 6 hours, dried at 120 ℃ overnight, and calcined at 450 ℃ for 3 hours to obtain calcined catalyst DC 1.
Comparative example 2 preparation of type II NiCoMo catalyst DC2 (not according to the invention)
Step 1, extruding, drying and roasting pseudo-boehmite to prepare clover-shaped A12O3And (3) a carrier.
Step 2, molybdenum trioxide (24g) and basic nickel carbonate (5g) were thermally dissolved in a hot phosphoric acid solution (8g) having a concentration of 85% to prepare a NiMoP solution. The NiMoP-CA (citric acid) mixed solution was added to 70g of the above carrier, and after impregnation, the extrudate was aged at room temperature for 6 hours and dried at 120 ℃.
And step 3, thermally dissolving molybdenum trioxide (24g) and cobalt hydroxide (6g) in a hot phosphoric acid solution (8g) with the concentration of 85% to prepare a CoMoP solution. After the catalyst precursor was impregnated with a CoMoP-CA (citric acid, citric acid/Mo ═ 0.1, molar ratio) mixed solution, it was aged at room temperature for 6 hours, and dried at 100 to 260 ℃ for 6 hours, to obtain catalyst DC2 of type II.
The catalyst used for evaluation was sulfurized with aviation kerosene fractions containing carbon disulfide at 260 ℃ and 370 ℃ for 8 hours, respectively, and after the feedstock oil was fed thereto, the feedstock oil was stabilized for 8 hours under the reaction conditions, and a hydrodenitrogenation reaction test was started. When the catalyst is evaluated, the denitrification rate is 95w percent by adjusting the reaction temperature, namely the nitrogen content in the generated oil is controlled to be 0.007w percent, and the denitrification rate can be achieved by controlling the reaction temperature of the catalyst to be low, which shows that the catalyst has higher hydrodenitrogenation activity. It can be seen that catalyst C4 of example 4 has the highest hydrodenitrogenation activity.
TABLE 1 Properties of the raw oils
| Raw oil | VGO |
| Density, g/ml | 0.9 |
| Sulfur, w% | 0.51 |
| Nitrogen, w% | 0.15 |
| Carbon residue, w% | 0.05 |
| Distillation range, deg.C | |
| IBP/10％ | 290/345 |
| 30％/50％ | 360/390 |
| 70％/90％ | 400/435 |
| 95％/EBP | 445/460 |
TABLE 2 hydrodenitrogenation reaction process conditions
| Reaction pressure, MPa | 7.0 |
| LHSV,h-1 | 1.0 |
| H2Oil ratio, V/V | 1000 |
TABLE 3 comparison of hydrodenitrogenation activity of catalysts
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a hydrotreating catalyst with denitrification activity is characterized by comprising the following steps:
step 1, preparing a porous carrier based on alumina or a phosphorus-containing alumina material;
step 2, impregnating the porous carrier with a metal I solution, curing, drying and roasting to obtain a catalyst precursor, wherein the metal I solution is a CoMoP solution containing Co, Mo and P elements;
step 3, dipping the catalyst precursor into a II-type metal solution containing an organic auxiliary agent, and then curing and drying the catalyst precursor without roasting to obtain a final catalyst; the II-type metal solution is a NiMoP solution containing Ni, Mo and P elements.
2. The method of claim 1, wherein the organic auxiliary agent in step 2 comprises an alcohol and/or an organic acid.
3. The method of claim 1, wherein the organic auxiliary in step 3 is selected from the group consisting of: the organic auxiliary agent is contained in an amount of 0.01 to 3 mol per mol of the active metal based on the metal II solution.
4. The method of claim 1, wherein the step 3 of drying is one or more times of drying.
5. The method of claim 1, wherein the drying temperature in step 3 is less than 260 ℃.
6. The method for producing a hydrotreating catalyst with denitrification activity according to claim 5, wherein the drying temperature in the step 3 is 100 to 260 ℃ C
7. The method of claim 2, wherein the alcohol-based organic auxiliary agent is polyethylene glycol.
8. The method of claim 2, wherein the organic acid-based organic auxiliary agent is citric acid.
9. The method of claim 1, wherein the ratio of the group I active sites to the group II active sites in the catalyst is in the range of 0.1 to 0.5.
10. The method for preparing a hydroprocessing catalyst with denitrification activity according to claim 1, wherein the drying temperature in step 2 is 100 to 300 ℃ and the calcination temperature is 400 to 550 ℃.
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| CN113430002B (en) * | 2020-03-23 | 2023-02-24 | 中国石油天然气股份有限公司 | Inferior wax oil hydrotreating method |
| CN113430003B (en) * | 2020-03-23 | 2023-02-28 | 中国石油天然气股份有限公司 | Hydrotreating method for base oil of lubricating oil |
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| CA2839881C (en) * | 2011-06-22 | 2020-08-18 | Shell Internationale Research Maatschappij B.V. | A hydroprocessing catalyst and methods of making and using such a catalyst |
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