CN112717963B - Hydrogenation pretreatment catalyst, and preparation method and application thereof - Google Patents

Hydrogenation pretreatment catalyst, and preparation method and application thereof Download PDF

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Publication number
CN112717963B
CN112717963B CN201911031653.5A CN201911031653A CN112717963B CN 112717963 B CN112717963 B CN 112717963B CN 201911031653 A CN201911031653 A CN 201911031653A CN 112717963 B CN112717963 B CN 112717963B
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catalyst
alumina powder
drying
roasting
magnesium
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CN112717963A (en
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王会刚
杨占林
姜虹
刘奕
丁思佳
王继锋
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J35/615—
    • B01J35/633—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Abstract

The invention discloses a hydrogenation pretreatment catalyst and a preparation method and application thereof, wherein the method comprises the following steps: (1) loading a magnesium-containing compound solution to the alumina powder a, and drying; (2) loading the phosphorus-containing compound solution to the alumina powder b, and drying; (3) forming, drying and roasting the dried alumina powder in the steps (1) and (2) to obtain a catalyst carrier; (4) and (3) loading active metal on the carrier obtained in the step (3), drying and roasting to obtain the final hydrogenation pretreatment catalyst, wherein the catalyst prepared by the method has the advantages of proper pore size, concentrated distribution, excellent stability and strong raw material adaptability, and can be used for the hydrogenation pretreatment process of poor hydrocarbon raw materials with high oxygen content, high nitrogen content, high aromatic hydrocarbon content and the like.

Description

Hydrogenation pretreatment catalyst, and preparation method and application thereof
Technical Field
The invention relates to a hydrogenation pretreatment catalyst, a preparation method and application thereof, in particular to a preparation method of a hydrogenation pretreatment catalyst which aims at hydrocarbon raw materials with the characteristics of high oxygen content, high nitrogen content, high aromatic hydrocarbon content and the like and has good coking resistance and hydrothermal performance.
Background
With the rapid development of economy in China, the demand for fuel oil and chemical raw materials is continuously increased, and the amount of crude oil processed each year is continuously increased. At the present stage, the processing of crude oil in China mostly depends on the import of foreign crude oil. Along with the increase of the exploitation amount of crude oil, the quality of the crude oil at home and abroad gradually becomes worse, and the trend of heaviness becomes more and more obvious. In order to meet the requirement of environmental protection and maximize the utilization of the existing resources, researchers have developed new technologies and catalysts for processing and utilizing inferior raw oil, coal liquefied oil, oil sand oil, fischer-tropsch synthetic oil and other similar natural petroleum oils, but hydrocarbon compounds containing more unsaturated hydrocarbons, oxygen, nitrogen and other elements than the natural petroleum oils. In processing several of these types of feedstocks, a large amount of hydrodeoxygenation is often associated with the process, which generates a large amount of water vapor that can seriously affect catalyst activity, stability and strength. In the processing process, the raw materials need to be subjected to deep hydrodenitrogenation so as to improve the quality of products. Raw materials like coal tar also have a large amount of aromatic hydrocarbons, and a catalyst is needed to realize deep hydrogenation and dearomatization. Therefore, the hydrogenation pretreatment catalyst needs to have better hydrogenation activity, stronger anti-coking performance and high hydrothermal stability to ensure that the device can run for a long period. The catalyst capable of meeting the requirements needs to have a high-activity active metal component, a proper acid center and pore channel structure and surface water resistance.
The patent CN104593058A discloses a coal tar hydrogenation catalyst and a preparation method thereof, wherein part of pseudo-boehmite is roasted at 800-1200 ℃, and the obtained powder is mixed with the non-roasted pseudo-boehmite and then mixed with an active metal component to prepare the hydrogenation pretreatment catalyst. The invention changes the structural property of partial carrier alumina powder through high-temperature roasting, so that the catalyst has larger pore volume, larger specific surface area and proper amount of macroporous structure. When the catalyst is used for coal tar hydrogenation pretreatment, the catalyst shows higher activity and stability. However, the excessive calcination results in a large loss of the whole acidic center of the carrier, which is not favorable for the hydrodenitrogenation of the catalyst.
Patent CN101069853A discloses an alumina carrier containing magnesium and phosphorus and a preparation method thereof. The carrier with low acidity, large pore volume and high specific surface area is prepared by adding three elements of magnesium, phosphorus and potassium in the synthesis process of the aluminum oxide. The carrier is suitable for the hydrogenation pretreatment process of hydrocarbons with the characteristics of high aromatic hydrocarbon content, high nitrogen content, high oxygen content and the like. The addition of the auxiliary agent in the preparation process is not favorable for the complete distribution of the auxiliary agent on the surface of the pore channel, and the relative utilization rate is low.
Patent CN1464031A discloses a coal tar hydro-upgrading catalyst, wherein the catalyst carrier contains 1-40 w% of titanium dioxide besides alumina. The pore volume and specific surface area of titanium dioxide are small, and the large amount of the component introduced into the carrier causes the performance of the pore structure of the catalyst to be reduced, so that the catalyst is not suitable for treating the coal tar component containing macromolecular aromatic hydrocarbon, colloid and asphaltene. With the addition of titanium, the surface acidity of the catalyst is enhanced, the coking phenomenon is more obvious, and the operation period of the catalyst is shortened.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a hydrogenation pretreatment catalyst, a preparation method and application thereof, wherein the catalyst has the advantages of proper pore size, centralized distribution, excellent stability and strong raw material adaptability, and can be used for the hydrogenation pretreatment process of hydrocarbons with high oxygen content, high nitrogen content, high aromatic hydrocarbon content and the like.
A preparation method of a hydrogenation pretreatment catalyst comprises the following steps:
(1) loading a magnesium-containing compound to the alumina powder a, and drying;
(2) loading a phosphorus-containing compound to the alumina powder b, and drying;
(3) forming, drying and roasting the dried alumina powder in the steps (1) and (2) to obtain a catalyst carrier;
(4) and (4) loading active metal on the carrier obtained in the step (3), and drying and roasting to obtain the final hydrogenation pretreatment catalyst.
In the method, the most probable pore diameter D of the alumina powder a is larger than the most probable pore diameter D of the alumina powder b, the preferred alumina powder b has the most probable pore diameter D of 7 nm-15 nm, and the difference between the most probable pore diameter D and the most probable pore diameter D is 8nm-15 nm, preferably 9 nm-12 nm.
In the above method, the two kinds of alumina powder may be commercially available or prepared according to the prior art. The preferred alumina powder a has a pore size distribution curve with only one peak, the corresponding most probable pore size is D, and the content of pores (corresponding pore volume, the same applies hereinafter) in the range of (D-5) nm to (D + 5) nm accounts for at least 87%, preferably 87% -95%, of the total content of pores.
In the above method, the preferred pore size distribution curve of the alumina powder b has only one peak, the corresponding most probable pore size is d, and the content of the pore channels in the range of (d-3) nm to (d + 3) nm at least accounts for 93%, preferably 93% -96%, of the total content of the pore channels.
In the above method, the two preferable alumina powder bodies have the following properties, in addition to the above pore channel structure, corresponding to the specific surface area and pore volume: a specific surface area of at least 190m2A/g, preferably of 200m2At least 0.36mL/g, preferably at least 0.39 mL/g.
In the above method, the magnesium-containing compound is a magnesium-containing organic compound, and may be one or more of magnesium acetate, magnesium oxalate, magnesium tartrate, magnesium stearate, magnesium citrate, and the like. The weight ratio of magnesium (calculated by oxide) in the alumina powder a is 0.1-7%, preferably 0.5-6%.
In the above method, the phosphorus-containing compound is one or more of phosphate or phosphite, and may be one or more of trilauryl phosphite, triphenyl phosphite, pentaerythritol diphosphite, alkyl (aryl) phosphate, fatty alcohol phosphate, alkylolamide phosphate, and the like. The weight ratio of phosphorus to alumina powder b is 0.4% to 6%, preferably 0.7% to 5%.
In the method, the content of the alumina powder a in the catalyst accounts for 30-60% of the total content of alumina by weight.
In the method, the drying temperature in the steps (1) and (2) is 60-120 ℃, preferably 70-110 ℃, and the drying time is 10-48 h, preferably 12-36 h.
In the method, extrusion aids, adhesives and peptizing agents can be added in the carrier forming process in the step (3). Suitable binder materials may be inorganic oxides such as a combination of one or more of titanium oxide, aluminum oxide, and zirconium oxide. The peptizing agent can be various organic acids, inorganic acids and can ionize to obtain H＋Such as nitric acid, hydrochloric acid, oxalic acid, acetic acid, propionic acid, ammonium dihydrogen phosphate, etc., and the peptizing agent used is one or more of the above-mentioned various substances.
In the method, the alumina powder containing the auxiliary agent is extruded into a selected shape in the step (3), and the catalyst carrier is prepared by drying and roasting. The catalyst can be made into various shapes according to the application requirements, such as spheres, tablets, rings, hollow cylinders or strips. Preferably in the form of strips (clover, cylindrical strips, etc.) and can be made in different sizes as required. The drying temperature is 80-150 ℃, preferably 90-140 ℃, and the drying time is 2-15 h, preferably 6-12 h.
The method, the roasting condition in the step (3): in inert gas, the roasting temperature is 300-550 ℃, preferably 350-530 ℃, and the roasting time is 3-10 h, preferably 5-8 h; suitable inert gases are preferably nitrogen or argon.
In the above method, the active metal component may be a metal of group vib or/and group viii, the metal of group vib is preferably molybdenum and/or tungsten, the metal of group viii is preferably nickel, and may be derived from a reagent such as a salt, an oxide or an acid containing the corresponding element, for example, molybdenum is typically one or more from molybdenum oxide, ammonium molybdate and ammonium paramolybdate, tungsten is typically from ammonium metatungstate, and nickel is from one or more from nickel nitrate, nickel carbonate, nickel hydroxycarbonate, nickel chloride and nickel oxalate. The configuration of the metal solution is well known to those skilled in the art.
In the method, the active metal component is loaded on the carrier by an impregnation method, and the active metal component can be impregnated in an equal volume or in an excessive amount; stepwise impregnation may be used, co-impregnation may also be used, preferably co-impregnation of equal volume. After impregnation, curing treatment is carried out, the curing temperature is 20-60 ℃, preferably 25-45 ℃, and the curing time is 4-24 h, preferably 6-18 h. Then, drying and roasting treatment are carried out. The drying temperature is 70-160 ℃, preferably 80-150 ℃, and the drying time is 2-16 h, preferably 5-12 h. The roasting atmosphere is air, the roasting temperature is 400-650 ℃, preferably 450-600 ℃, the roasting time is 0.5-7 h, preferably 1-6 h, the heating rate is 0.5-4 ℃, preferably 1-3 ℃.
The hydrotreating catalyst prepared by the method has the carbon content of 0.5-2 percent, VIB group metal oxide 10-30 percent and VIII group metal oxide 2-6 percent based on the weight of the catalyst. The specific surface area of the catalyst was 110m2/g～290m2A ratio of 125 m/g is preferred2/g～235m2(ii)/g; the pore volume is 0.22mL/g to 0.58mL/g, preferably 0.23mL/g to 0.53 mL/g.
The catalyst is used in the hydrogenation pretreatment process, applicable raw materials can be various inferior raw oil, including coal liquefied oil, oil sand oil, Fischer-Tropsch synthetic oil and the like, and the raw materials have the characteristics of high oxygen content, high nitrogen content, high aromatic hydrocarbon content and the like.
The reaction conditions of the catalyst are as follows: 8 MPa-20 MPa, reaction temperature of 350-450 ℃, and feeding volume airspeed of 0.6-2.0 h-1The volume ratio of hydrogen to oil is 500: 1-2000: 1.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the catalyst of the invention introduces magnesium element into the large-aperture alumina, effectively reduces the surface acidity of the catalyst, enhances the anti-coking performance, and ensures the high-efficiency mass transfer of macromolecular substances in a large pore channel of the catalyst.
(2) The catalyst of the invention introduces phosphorus element into the alumina with small aperture, effectively improves the structural stability of the catalyst, and avoids local coking caused by the collapse of some structures.
(3) The catalyst of the invention introduces organic species of magnesium and phosphorus, and the carbon layer formed by high-temperature carbonization effectively reduces the migration of magnesium and phosphorus and ensures the uniformity of the dispersion of the magnesium and phosphorus.
(4) The carbon layer formed in the preparation process of the catalyst can weaken the interaction between the metal and the carrier, inhibit the sintering of the active metal of the catalyst and improve the activity of the catalyst. The residual carbon in the final catalyst can not only increase the surface hydrophobicity of the catalyst and improve the water resistance of the catalyst, but also fill a part of micropores in the catalyst, prevent the active metal from dispersing to the position which can not be contacted, and improve the utilization rate of the catalyst.
Detailed Description
The hydrogenation pretreatment catalyst of the invention loads two organic compounds with different assistants to alumina powder with different pore sizes, and then the alumina powder is obtained by full rolling, molding and specific roasting processes, then loads metal components, and is obtained by curing, drying and conventional roasting.
In the embodiment, the magnesium-containing organic compound is magnesium citrate, the phosphorus-containing organic compound is octadecyl phosphate, and the metal component is tungsten nickel, and the preparation process of the catalyst is as follows:
(1) dipping the alumina powder a by using a magnesium citrate aqueous solution; the alumina powder b was impregnated with an aqueous octadecyl phosphate solution. The two kinds of powder are dried for 18h at the temperature of 90 ℃.
(2) Mixing the two kinds of alumina powder modified with the assistant for 15min in kneading machine, rolling machine, etc; slowly adding binder and/or peptizing agent solution into the mixed powder, mixing or grinding for 20min to form plastic body, and extruding into 1.7mm clover strip.
(3) The molding material is dried for 8 hours at the temperature of 110 ℃, and then is roasted for 6 hours at the temperature of 500 ℃ in the nitrogen atmosphere to obtain the carrier.
(4) After a carrier is impregnated by a metal solution containing a W-Ni component, curing is carried out for 12h at the temperature of 30 ℃, then drying is carried out for 8h at the temperature of 120 ℃, then the temperature is raised to the set temperature at the speed of 1 ℃/min in the air atmosphere, and the final hydrogenation pretreatment catalyst is obtained by roasting.
And (3) measuring the pore structure of the calcined hydrotreating catalyst by using a low-temperature nitrogen physical adsorption method.
The technical features of the catalyst of the present invention are further described below by way of examples, but the present invention should not be construed as being limited to only these examples. The percentage of the material is weight percentage.
The pore structure properties of the alumina powder a used in the examples were: pore volume of 0.92cm3393m of specific surface area per gram2The pore channel content of the most probable pore size of 22nm and the range of 17nm to 27nm accounts for 92 percent of the total pore channel content.
The pore structure properties of the alumina powder b used in the examples were: the pore volume is 0.65cm3Per g, specific surface area of 335m2The pore size of the most probable pore size is 13nm, and the content of the pore channels between 10nm and 16nm accounts for 96 percent of the total pore channels.
Example 1
Weighing the powder according to the proportion that the alumina powder a accounts for 30 percent of the total weight of the alumina. Weighing magnesium citrate according to the weight of magnesium oxide accounting for 4 percent of the weight of the alumina powder a to prepare an aqueous solution, and soaking the alumina powder a in the same volume; and weighing octadecyl phosphate to prepare an aqueous solution according to the weight of phosphorus accounting for 3.5 percent of the weight of the alumina powder b, and soaking the alumina powder b in the same volume. Drying the alumina powder loaded by the auxiliary agent for 18h at 90 ℃. Mixing the alumina powder modified by the two additives, citric acid accounting for 2.3 percent of the weight of the alumina and sesbania powder accounting for 3.6 percent of the weight of the alumina uniformly, adding an acid solution, wherein the concentration of nitric acid in the acid solution is 2.3 percent by weight, and the balance is distilled water. Mixing in a kneading machine for 15min to form plastic body, and extruding into 1.7mm clover strips. The molding material is dried for 8 hours at the temperature of 110 ℃, and then is roasted for 6 hours at the temperature of 500 ℃ in the nitrogen atmosphere to obtain the carrier. Calculated according to the weight of the catalyst: 4 percent of nickel oxide and 25 percent of tungsten oxide are prepared into tungsten-nickel metal solution. Equal volume of tungsten nickel solution was impregnated onto the support strip. Curing the active metal loaded alumina powder at 30 ℃ for 12 h. Drying at 120 ℃ for 8h, and roasting at 500 ℃ for 3h to obtain the catalyst Cat-1.
Example 2
Weighing the alumina powder a accounting for 43 percent of the total weight of the alumina. The other subsequent steps are the same as example 1, and catalyst Cat-2 is obtained.
Example 3
Weighing the powder according to the proportion that the alumina powder a accounts for 60 percent of the total weight of the alumina. The other subsequent steps are the same as example 1, and catalyst Cat-3 is obtained.
Example 4
Weighing the powder according to the proportion that the alumina powder a accounts for 43 percent of the total weight of the alumina, carrying out the same other subsequent steps as in example 2, and roasting at 450 ℃ for 4h after loading metal to obtain the catalyst Cat-4.
Example 5
Weighing the powder according to the proportion that the alumina powder a accounts for 43 percent of the total weight of alumina, carrying out the same other subsequent steps as in example 2, and roasting at 550 ℃ for 2.5h after loading metal to obtain the catalyst Cat-5.
Example 6
Weighing the powder according to the proportion that the alumina powder a accounts for 43 percent of the total weight of the alumina, and roasting the powder for 3 hours at 500 ℃ in the air atmosphere in the subsequent powder modification step which is the same as the embodiment 2. Then, the steps of molding, metal loading, curing, drying, roasting and the like are the same as in example 2, and the final catalyst Cat-6 is obtained.
Comparative example 1
Weighing the alumina powder a and the alumina powder b according to the proportion of the alumina powder used in the embodiment 2, mixing and molding, wherein the steps and the dosage are the same as those of the embodiment 2, then impregnating the prepared carrier with the metal solution with the same proportion as that of the embodiment 2, drying at 120 ℃ for 10h, and roasting at 500 ℃ for 3h to obtain the catalyst DC-1.
Example 7
Evaluation test of catalytic Performance of catalyst: before evaluation, CS was used2The cyclohexane solution treatment catalyst has the concentration of 3.5wt%, the vulcanization temperature of 340 ℃, the pressure of 6Mpa, the vulcanization time of 6h and the corresponding volume ratio of the hydrogen to the vulcanization solution of 550.
Coal tar is used as a raw material, the activity evaluation of the catalyst is carried out on a micro-reaction device with the catalyst loading of 20mL, the reaction temperature is 370 ℃, the reaction pressure is 13Mpa, and the airspeed is 0.8h-1The volume ratio of hydrogen to oil was 1000.
TABLE 1 Properties of the stock oils
Figure 872594DEST_PATH_IMAGE002
TABLE 2 catalyst Properties and catalytic Effect of examples and comparative examples
Figure 720333DEST_PATH_IMAGE004
Relative activity was based on comparative example DC-1.

Claims (10)

1. A preparation method of a hydrogenation pretreatment catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) loading a magnesium-containing compound to the alumina powder a, and drying;
(2) loading a phosphorus-containing compound to the alumina powder b, and drying;
(3) forming, drying and roasting the dried alumina powder in the steps (1) and (2) to obtain a catalyst carrier;
(4) loading active metal on the carrier obtained in the step (3), drying and roasting to obtain the final hydrogenation pretreatment catalyst;
the magnesium-containing compound is one or more of magnesium acetate, magnesium oxalate, magnesium tartrate, magnesium stearate and magnesium citrate; magnesium accounts for 0.1 to 7 percent of the weight of the alumina powder a in terms of oxide;
the phosphorus-containing compound is one or more of trilauryl phosphite, triphenyl phosphite, pentaerythritol diphosphite, alkyl (aryl) phosphate, fatty alcohol phosphate and alkylolamide phosphate, and phosphorus accounts for 0.4-6% of the weight of the alumina powder b;
the most probable pore diameter D of the alumina powder a is larger than the most probable pore diameter D of the alumina powder b, the most probable pore diameter D of the alumina powder b is 7 nm-15 nm, and the difference between the most probable pore diameter D and the D is 8nm-15 nm;
the weight content of the alumina powder a in the catalyst accounts for 30-60% of the total mass of the alumina in the final catalyst.
2. The method of claim 1, wherein: the drying temperature in the steps (1) and (2) is 60-120 ℃, and the drying time is 10-48 h.
3. The method of claim 1, wherein: and (3) adding an extrusion aid, an adhesive or a peptizing agent in the carrier forming process, wherein the peptizing agent is one or more of nitric acid, hydrochloric acid, oxalic acid, acetic acid, propionic acid and ammonium dihydrogen phosphate.
4. The method of claim 1, wherein: and (4) preparing the catalyst in the step (3) into a spherical shape, a tablet shape, a ring shape, a hollow cylinder shape or a strip shape according to the application requirement.
5. The method of claim 1, wherein: the roasting condition in the step (3) is as follows: in inert gas, the roasting temperature is 300-550 ℃, and the roasting time is 3-10 h; the inert gas is nitrogen or argon.
6. The method of claim 1, wherein: in the step (4), the active metal is a metal in a VIB group or/and a VIII group.
7. The method of claim 6, wherein: the VIB group metal is molybdenum and/or tungsten, the VIII group metal is nickel, the molybdenum is one or more of molybdenum oxide, ammonium molybdate and ammonium paramolybdate, the tungsten is ammonium metatungstate, and the nickel is one or more of nickel nitrate, nickel carbonate, basic nickel carbonate, nickel chloride and nickel oxalate.
8. The method of claim 1, wherein: in the step (4), active metal is loaded on the carrier by an impregnation method, and equal-volume impregnation or excessive impregnation is adopted; after dipping, carrying out curing treatment, wherein the curing temperature is 20-60 ℃, and the curing time is 4-24 h.
9. The method of claim 1, wherein: in the step (4), the drying temperature is 70-160 ℃, the drying time is 2-16 h, the roasting atmosphere is air, the roasting temperature is 400-650 ℃, and the roasting time is 0.5-7 h.
10. A hydroprocessing catalyst prepared by the process of any of claims 1 through 9, characterized by: based on the weight of the catalyst, 10 to 30 percent of VIB group metal oxide and 2 to 6 percent of VIII group metal oxide, and the specific surface area of the catalyst is 110m2/g～290m2(ii)/g; the pore volume is 0.22 mL/g-0.58 mL/g.
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