CN105749924B - A kind of heavy oil hydrogenating treatment catalyst and its application - Google Patents

Abstract

The invention provides a heavy oil hydrotreating catalyst, which comprises a boron-containing shaped alumina carrier, a metal component molybdenum, and a metal component cobalt or nickel; calculated as an oxide and based on the total weight of the boron-containing shaped alumina carrier As a benchmark, the content of boron in the boron-containing shaped alumina carrier is 0.5-5% by weight; calculated as an oxide and based on the load on the surface of a unit carrier, the content of molybdenum in the metal component in the catalyst is 4.8 μmol/m ² -9.0μmol/m ² , the content of the metal component cobalt or nickel is 1.5μmol/m ² -4.0μmol/m ² ; when the catalyst is characterized by XRD, the diffraction angle 2θ=26°± 2 ° no MoO ₃ characteristic peak appears. Compared with the existing heavy oil hydrotreating catalyst, the heavy oil hydrotreating catalyst of the present invention has better hydrodesulfurization, denitrogenation and carbon residue removal effects when the heavy oil hydrotreating is carried out.

Description

A catalyst for heavy oil hydrotreating and its application

technical field

The invention relates to a heavy oil hydrogenation treatment catalyst and a heavy oil hydrogenation treatment method using the heavy oil hydrogenation treatment catalyst.

Background technique

Heavy oil processing, especially the deep processing of residual oil, not only helps to improve the utilization rate of crude oil, alleviate the tense trend of energy supply, but also reduce environmental pollution and realize efficient and clean utilization of energy.

Heavy oil is enriched with impurities such as sulfur, nitrogen, metals, and carbon residues in crude oil. These impurities have serious adverse effects on subsequent processing and product properties, so they must be removed. Since impurities such as sulfur and nitrogen in heavy oil are mostly enriched in macromolecular polycyclic aromatic hydrocarbons, it is difficult to remove them. Therefore, catalysts for related reactions such as desulfurization, denitrogenation, and carbon residue removal are required to have high catalytic activity. . The reactivity of the catalyst is directly related to the number of active centers on the surface of the catalyst, and more active centers on the surface will be beneficial to the improvement of the reactivity of the catalyst. The increase of active centers on the catalyst surface cannot be simply achieved by increasing the amount of active metal on the catalyst (i.e., the loading amount of the metal component), because increasing the amount of metal on the conventional catalyst preparation method will lead to metal aggregation, which will reduce the utilization rate of the active metal. . Therefore, improving the dispersion state of active metals, avoiding the aggregation of active metals, and improving the utilization of active metals are the key to the development of high-performance heavy oil desulfurization and carbon residue removal catalysts.

Patent ZL201110187353.3 discloses a hydrorefining catalyst, which is a three-component catalyst of molybdenum, cobalt and nickel supported on a titanium-modified alumina carrier, wherein the content of molybdenum oxide is 4-18% by weight , the content of nickel oxide is 0.2-5%, and the content of cobalt oxide is 2.0-7.5%. The specific preparation method is that the carrier is impregnated with a co-impregnation solution containing molybdenum, nickel and cobalt, dried and activated and roasted.

The nickel-molybdenum or cobalt-molybdenum catalysts disclosed in the prior art are not easy to have a high active metal content due to the aggregation between metals, especially the content of active molybdenum oxide cannot be increased, which leads to a limited number of active centers on the catalyst surface, affecting enhanced catalyst reactivity.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new catalyst with high metal content which cannot avoid the aggregation of active metals, which leads to the reduction of active centers on the surface of the catalyst. A heavy oil hydrotreating catalyst with better desulfurization, denitrification effect and carbon residue conversion performance and its application.

In order to achieve the above object, the present invention provides a heavy oil hydrotreating catalyst, which comprises a boron-containing shaped alumina carrier, a metal component molybdenum, and a metal component cobalt or nickel; Based on the total weight of the aluminum carrier, the content of boron in the boron-containing shaped alumina carrier is 0.5-5% by weight; calculated as an oxide and based on the load on the surface of the unit carrier, the metal component in the catalyst The content of molybdenum is 4.8 μmol/m ² -9.0 μmol/m ² , the content of the metal component cobalt or nickel is 1.5 μmol/m ² -4.0 μmol/m ² ; when the catalyst is characterized by XRD, the diffraction angle 2θ=26°±2°, no characteristic peak of MoO ₃ appears.

Preferably, wherein, calculated as oxides and based on the load on the surface of the unit carrier, the content of the metal component molybdenum in the catalyst is 5.4 μmol/m ² -8.0 μmol/m ² , and the metal component cobalt Or the nickel content is 1.8 μmol/m ² -3.6 μmol/m ² .

Preferably, wherein, calculated as oxides and based on the load on the surface of the unit carrier, the content of the metal component molybdenum in the catalyst is 5.9 μmol/m ² -7.5 μmol/m ² , and the metal component cobalt Or the nickel content is 2.0 μmol/m ² -3.1 μmol/m ² .

Preferably, the boron-containing shaped alumina support is subjected to hydrothermal treatment under airtight conditions before loading the metal component molybdenum and the metal component cobalt or nickel.

Preferably, wherein, the temperature of the hydrothermal treatment is 60-180° C., and the time is 1-24 hours; by weight, the amount of water used in the hydrothermal treatment is 100-300% by weight of the weight of the boron-containing shaped alumina carrier .

Preferably, the boron-containing shaped alumina carrier that has undergone the hydrothermal treatment is subjected to drying treatment before loading the metal component molybdenum and the metal component cobalt or nickel; the temperature of the drying treatment is 60- 350°C, the drying time is 1-48 hours.

Preferably, wherein, the preparation step of the boron-containing shaped alumina carrier comprises: introducing a boron-containing element compound into an alumina precursor, and then shaping the alumina precursor into which the boron-containing element compound is introduced, and Calcining the shaped alumina precursor.

Preferably, the boron-containing shaped alumina support has at least one crystal phase selected from γ-, η-, θ-, δ- and χ-alumina crystal phases.

Preferably, the boron-containing shaped alumina carrier is at least one shape selected from the group consisting of spherical, cylindrical, ring, clover, quatrefoil, honeycomb and butterfly.

Preferably, wherein the metal component molybdenum and the metal component cobalt or nickel are supported on the boron-containing shaped alumina carrier by impregnation.

Preferably, wherein the impregnated boron-containing shaped alumina carrier is subjected to drying treatment and calcination treatment or no calcination treatment; the temperature of the drying treatment is 60-150° C., and the drying treatment time is 1-5 hours; The temperature of the roasting treatment is 350-550° C., and the time of the roasting treatment is 1-6 hours.

The present invention also provides a heavy oil hydrotreating method, the method comprising: under heavy oil hydrotreating conditions, heavy oil is contacted with the heavy oil hydrotreating catalyst provided by the present invention and the heavy oil is hydrotreated.

Preferably, according to the heavy oil hydrotreating method of the present invention, wherein, the heavy oil is at least one selected from crude oil, atmospheric residue, vacuum residue, deep waxed oil, light deasphalted oil and coker wax oil kind.

Preferably, according to the heavy oil hydrotreating method of the present invention, the heavy oil hydrotreating conditions include: a reaction temperature of 300-550°C, a hydrogen partial pressure of 4-20 MPa, and a liquid hourly space velocity of 0.1-3 hours ^-1 , the volume ratio of hydrogen to oil is 200-2500.

Compared with the existing heavy oil hydrotreating catalyst, the heavy oil hydrotreating catalyst of the present invention has better hydrodesulfurization, denitrogenation and carbon residue removal effects when the heavy oil hydrotreating is carried out.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is the XRD spectrogram of the heavy oil hydrotreating catalyst C1 provided by the present invention (i.e. the catalyst prepared in Example 3);

Fig. 2 is the XRD spectrum of the heavy oil hydrotreating catalyst DC1 (ie the catalyst prepared in Comparative Example 1) prepared by the prior art.

Detailed ways

Specific embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The invention provides a heavy oil hydrotreating catalyst, which comprises a boron-containing shaped alumina carrier, a metal component molybdenum, and a metal component cobalt or nickel; calculated as an oxide and based on the total weight of the boron-containing shaped alumina carrier As a benchmark, the content of boron in the boron-containing shaped alumina carrier is 0.5-5% by weight; calculated as an oxide and based on the load on the surface of a unit carrier, the content of molybdenum in the metal component in the catalyst is 4.8 μmol/m ² -9.0 μmol/m ² , preferably 5.4 μmol/m ² -8.0 μmol/m ² , more preferably 5.9 μmol/m ² -7.5 μmol/m ² , the content of the metal component cobalt or nickel 1.5 μmol/m ² -4.0 μmol/m ² , preferably 1.8 μmol/m ² -3.6 μmol/m ² , more preferably 2.0 μmol/m ² -3.1 μmol/m ² ; when the catalyst is characterized by XRD, No characteristic peak of MoO ₃ appears at the diffraction angle 2θ=26°±2°. Wherein, the unit carrier surface loading refers to the loading on the unit surface area of the carrier, that is, the ratio of the loading of the metal component in the catalyst to the total surface area of the carrier. A boron-shaped alumina carrier, if the boron-containing shaped alumina carrier has undergone hydrothermal treatment before loading metal components, the carrier refers to a boron-containing shaped alumina carrier before hydrothermal treatment. The size of the total surface area of the carrier is determined by the BET method according to the RIPP151-90 standard method.

The inventors of the present invention unexpectedly found that when the heavy oil hydrotreating catalyst of the present invention was characterized by XRD, no characteristic peak of MoO ₃ appeared at the diffraction angle 2θ=26°±2°. This explanation is different from the heavy oil hydrotreating catalyst of existing high molybdenum content, the molybdenum trioxide in the catalyst of the present invention is dispersed better on the catalyst surface, does not gather in a large amount, thereby can't detect MoO _The characteristic peak, and Such catalysts have high reactivity.

According to the heavy oil hydrotreating catalyst of the present invention, the boron-containing shaped alumina carrier may undergo hydrothermal treatment under closed conditions before loading the metal component molybdenum and the metal component cobalt or nickel. The hydrothermal treatment is different from the conventional catalyst high-temperature water vapor treatment in that the hydrothermal treatment of the boron-containing shaped alumina carrier in the present invention refers to putting the boron-containing shaped alumina carrier and water into a closed container such as a reaction kettle, and then Heating to a certain temperature under certain conditions, and then carrying out hydrothermal treatment at the hydrothermal treatment temperature. The boron-containing shaped alumina support after hydrothermal treatment can make the supported metal components present a better dispersed state, and improve the number of active centers and catalytic activity of the prepared catalyst. Wherein, the temperature of the hydrothermal treatment can be 60-180°C, preferably 90-150°C; the time of the hydrothermal treatment can be 1-24 hours, preferably 4-12 hours; by weight, in the hydrothermal treatment The amount of water used may be 100-300% by weight of the weight of the boron-containing shaped alumina carrier, preferably 150-250% by weight of the weight of the boron-containing shaped alumina carrier. In the present invention, the pressure of the hydrothermal treatment is autogenous pressure under airtight conditions. When the hydrothermal treatment is carried out at a constant temperature, the hydrothermal treatment temperature is the constant temperature temperature, and the time of the hydrothermal treatment is from the airtight container to the The timing starts at the hydrothermal treatment temperature; the heating rate of the heating process before the hydrothermal treatment is not particularly limited, preferably 5-15°C/min, more preferably 8-12°C/min.

According to the heavy oil hydrotreating catalyst of the present invention, the boron-containing shaped alumina carrier that has undergone the hydrothermal treatment can also be dried before loading the metal component molybdenum and the metal component cobalt or nickel, so as to Remove moisture from the alumina surface and pores. The conditions of the drying treatment are not particularly limited, and may be selected conventionally in the field, as long as the moisture on the surface of the alumina and in the pores can be removed. Generally, the drying treatment can be carried out at a temperature of 60-350°C, preferably at a temperature of 80-200°C, more preferably at a temperature of 100-150°C. The time of the drying treatment can be appropriately selected according to the temperature of the drying treatment, and is not particularly limited. Generally, the drying time may be 1-48 hours, preferably 1-24 hours, more preferably 1-8 hours.

According to the heavy oil hydrotreating catalyst of the present invention, wherein, the preparation step of the boron-containing shaped alumina support may include: introducing a boron-containing compound into the precursor of alumina, and then introducing the boron-containing compound The alumina precursor is shaped, and the shaped alumina precursor is fired. The boron-containing compound may be at least one selected from any boron-containing oxide, acid, alkali and salt. Since the boron-containing shaped alumina carrier of the present invention contains less boron element, the boron-containing shaped alumina carrier generally maintains the crystal phase of pure alumina. The alumina crystal phase is well known to those skilled in the art, for example, the boron-containing shaped alumina support may have at least one of the alumina crystal phases of γ-, η-, θ-, δ- and χ- seed phase.

According to the heavy oil hydrotreating catalyst of the present invention, according to the specific use requirements of the catalyst, molding tools such as extruders can be used to shape the alumina precursor introduced with the boron-containing compound. This is the preparation process of the hydrotreating catalyst. For example, the boron-containing shaped alumina carrier can be in at least one shape selected from spherical, cylindrical, ring, clover, quatrefoil, honeycomb and butterfly.

According to the heavy oil hydrotreating catalyst of the present invention, the method for loading metal components on the carrier is well known to those skilled in the art, for example, the metal component molybdenum and the metal component cobalt or nickel can be loaded by impregnation On the boron-containing shaped alumina support, that is, impregnating the boron-containing shaped alumina support with a solution of a molybdenum-containing metal component compound and a cobalt- or nickel-containing metal component compound. Wherein, the molybdenum-containing metal component compound can be selected from one or more of its soluble compounds, such as one or more of molybdenum oxide, molybdate and paramolybdate, preferably molybdenum oxide wherein One or more of ammonium molybdate and ammonium paramolybdate; the compound containing cobalt or nickel metal components can be selected from one or more of their soluble compounds, such as cobalt nitrate, cobalt acetate , one or more of basic cobalt carbonate, cobalt chloride, soluble complexes of cobalt, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel soluble complexes, preferably from cobalt nitrate One or more of basic cobalt carbonate, nickel nitrate and basic nickel carbonate. The impregnation is well known to those skilled in the art, and can be equal impregnation or excessive impregnation, co-impregnation or step-by-step impregnation, for example, solutions containing individual metal component compounds can be used respectively Impregnation of the boron-containing shaped alumina carrier can also be impregnated with a boron-containing shaped alumina carrier with a mixed solution containing a variety of metal component compounds. Those skilled in the art can control the content of the metal component introduced into the catalyst by adjusting the concentration of the impregnating solution containing the metal component compound and the amount of the impregnating solution during the impregnation process, which will not be repeated here.

According to the heavy oil hydrotreating catalyst of the present invention, the impregnated boron-containing shaped alumina carrier can also be dried and roasted or not roasted. The methods and conditions of the drying treatment and roasting treatment are well known to those skilled in the art, for example, the temperature of the drying treatment can be 60-150°C, preferably 80-120°C; the time of the drying treatment can be 1-5 hours, It is preferably 2-4 hours; the temperature of the calcination treatment may be 350-550°C, preferably 400-500°C; the time of the calcination treatment may be 1-6 hours, preferably 2-4 hours.

The heavy oil hydrotreating catalyst provided by the present invention can be used alone or in combination with other catalysts. The catalyst is especially suitable for the hydrotreating of heavy oil, especially inferior residue oil, so as to provide qualified of raw oil.

The present invention also provides a heavy oil hydrotreating method, the method comprising: under heavy oil hydrotreating conditions, heavy oil is contacted with the heavy oil hydrotreating catalyst provided by the present invention and the heavy oil is hydrotreated.

In the present invention, the heavy oil may be various heavy oil feedstocks that require hydroprocessing, preferably various heavy hydrocarbon feedstocks that require hydrodesulfurization, denitrogenation, and residual carbon removal. Specifically, the heavy oil may be at least one selected from crude oil, atmospheric residual oil, vacuum residual oil, deep waxed oil, light deasphalted oil and coker waxed oil. The method for hydrotreating heavy oil of the present invention is to carry out hydrotreating to heavy oil with higher efficiency by contacting heavy oil with the catalyst provided by the present invention. properties, and make appropriate selections based on conventional knowledge in the field. For example, the heavy oil hydrotreating conditions may be as follows: the reaction temperature is 300-550 °C, the hydrogen partial pressure is 4-20 MPa, the liquid hourly space velocity is 0.1-3 h ^-1 , and the hydrogen-to-oil volume ratio is 200-2500; The heavy oil hydrotreating conditions are preferably as follows: reaction temperature 350-450°C, hydrogen partial pressure 8-16 MPa, liquid hourly space velocity 0.15-2h- ¹ , hydrogen-to-oil volume ratio 400-2000.

The heavy oil hydrotreating can be carried out in any reactor sufficient to make the heavy oil contact with the heavy oil hydrotreating catalyst under heavy oil hydrotreating conditions and carry out heavy oil hydrotreating, for example, it can be in a fixed bed reactor , moving bed reactor or ebullating bed reactor.

According to the heavy oil hydrotreating method of the present invention, the catalyst can be presulfurized under conventional conditions in the art before use. The presulfurization conditions can be: in the presence of hydrogen, the catalyst is presulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 140-370 ° C. The presulfurization can be carried out outside the reactor or in the In-situ sulfurization in the reactor.

The present invention will be further described by the following examples, but the present invention is not limited thereto.

The reagents used in the following examples and comparative examples are chemically pure reagents unless otherwise specified.

In the following examples and comparative examples, adopt the method specified in RIPP 25-90 to measure the radial crushing strength of the carrier; adopt the method specified in RIPP 151-90 to measure the total surface area of the carrier, the pore volume of the carrier and the probability of the carrier. Pore diameter; The content of molybdenum, nickel and cobalt of the catalyst is measured by X-ray fluorescence spectrometry (i.e. XRF) in RIPP133-90; The boron content of the catalyst is measured by plasma emission spectrometry in RIPP128-90; here and For details of the RIPP standard method mentioned below, please refer to "Petrochemical Analysis Methods", edited by Yang Cuiding et al., 1990 edition.

In the following examples and comparative examples, the distribution state of active metal components in the catalyst is measured by X-ray powder diffractometer to confirm whether molybdenum trioxide is formed and aggregated. The instrument adopts Philips XPERT series X-ray powder diffractometer, and the test conditions are: Cu Kα X-ray (λ=0.154nm), Ni filter, voltage 40kV, current 30mA, scanning range 5-70°.

Examples 1-2 provide boron-containing shaped alumina supports of the present invention.

Example 1

The pseudo-boehmite dry rubber powder RPB90 produced by 1 kilogram of Changling Catalyst Factory and the turmeric powder of 30 grams are mixed uniformly. ) in 1.1 liters of aqueous solution, mixed evenly, continued kneading on a twin-screw extruder to form a plastic body, extruded into a trilobal strip of ф1.1 mm, dried at 120°C for 3 hours, and then roasted at 600°C for 3 hours to obtain Boron-containing shaped alumina carrier Z1. The physical and chemical results of the determination of Z1 are shown in Table 1.

Example 2

The pseudo-boehmite dry rubber powder RPB100 produced by 1 kilogram of Changling Catalyst Factory is mixed with 30 gram of turnip powder, at room temperature this mixture is mixed with boron trioxide 20g, nitric acid 25 milliliters (mass fraction 65%) Mix 1.2 liters of the aqueous solution of the solution evenly, continue kneading on the twin-screw extruder to form a plastic body, and extrude it into a butterfly-shaped strip of ф1.1 mm. After the wet strip is dried at 110°C for 2 hours, it is roasted at 700°C for 3 hours to obtain boron-containing Shaped alumina support Z2. The physical and chemical results of the determination of Z2 are shown in Table 1.

Examples 3-6 provide heavy oil hydroprocessing catalysts of the present invention.

Example 3

Weigh 150g of the Z1 carrier and place it in a hydration kettle, add 450g of deionized water, seal the hydration kettle and put it in an oven, heat it up with a program, control the heating rate to 10°C·min ^-1 , treat at 80°C, and take 12 hours. After the completion of the hydrothermal treatment, the alumina was filtered, and then dried at 120° C. for 3 hours to obtain a hydrothermally treated alumina carrier.

Take 100 grams of carrier Z1 after hydrothermal treatment, impregnate with 220 ml of ammonium molybdate and nickel nitrate mixed solution containing MoO ₃ 170 g/L, NiO 30 g/L for 1 hour, filter and dry at 120°C for 2 hours, then bake at 410°C After 4 hours, catalyst C1 was obtained. Calculated by oxide and based on the load on the surface of the unit carrier, the content of molybdenum oxide and nickel oxide in catalyst C1 is measured by X-ray fluorescence spectrometer, and whether molybdenum trioxide is formed in catalyst C1 by X-ray powder diffractometer. Determination The results are shown in Table 2, and the XRD spectrum of catalyst C1 is shown in FIG. 1 .

Example 4

Weigh 150g of the Z1 carrier and place it in a hydration kettle, add 150g of deionized water, seal the hydration kettle and put it in an oven, heat it up with a program, control the heating rate to 10°C·min ^-1 , and treat at 100°C for a time of 8 hours. After the completion of the hydrothermal treatment, the alumina was filtered, and then dried at 120° C. for 3 hours to obtain a hydrothermally treated alumina carrier.

Take 100 grams of carrier Z1 after hydrothermal treatment, impregnate it with 110 milliliters of MoO ₃ 260 g/L, CoO58 g/L molybdenum oxide, basic cobalt carbonate mixed solution for 0.5 hours, dry at 120°C for 2 hours, and bake at 450°C After 2 hours, catalyst C2 was obtained. Calculated by oxide and based on the load on the surface of the unit carrier, the content of molybdenum oxide and cobalt oxide in catalyst C2 was measured by X-ray fluorescence spectrometer, and whether molybdenum trioxide was formed in the catalyst by X-ray powder diffractometer. The measurement results As shown in table 2.

Example 5

Weigh 150g of the Z2 carrier and place it in a hydration kettle, add 225g of deionized water, seal the hydration kettle and put it in an oven, heat it up with a program, control the heating rate to 10°C·min ^-1 , treat at 120°C, and take 6 hours. After the completion of the hydrothermal treatment, the alumina was filtered, and then dried at 110° C. for 3 hours to obtain a hydrothermally treated alumina carrier.

Take 100 grams of carrier Z2 after hydrothermal treatment, impregnate it with 120 milliliters of molybdenum oxide and basic nickel carbonate mixed solution containing MoO ₃ 290 g/L, NiO 63 g/L for 1 hour, dry at 120°C for 2 hours, and dry at 480°C Calcined for 4 hours to obtain catalyst C3. Calculated by oxide and based on the load on the surface of the unit carrier, the content of molybdenum oxide and nickel oxide in catalyst C3 was measured by X-ray fluorescence spectrometer, and whether there was molybdenum trioxide in the catalyst was determined by X-ray powder diffractometer. The measurement results As shown in table 2.

Example 6

Weigh 150g of the Z2 carrier and place it in a hydration kettle, add 375g of deionized water, seal the hydration kettle and put it in an oven, heat it up with a program, control the temperature rise rate to 10°C·min ^-1 , and treat at 150°C for a time of 4 hours. After the completion of the hydrothermal treatment, the alumina was filtered, and then dried at 110° C. for 3 hours to obtain a hydrothermally treated alumina carrier.

Take 100 grams of carrier Z2 after hydrothermal treatment, impregnate it with 220 milliliters of molybdenum oxide and basic cobalt carbonate mixed solution containing MoO ₃ 260 g/L and CoO 41 g/L for 1 hour, filter and dry at 110°C for 3 hours, 450 ℃ for 2 hours to obtain catalyst C4. Calculated by oxide and based on the load on the surface of the unit carrier, the content of molybdenum oxide and cobalt oxide in the catalyst C4 was measured by X-ray fluorescence spectrometer, and whether molybdenum trioxide was formed in the catalyst by X-ray powder diffractometer. The measurement results As shown in table 2.

Comparative Examples 1-3 provide heavy oil hydrotreating catalysts prepared by existing methods.

Comparative example 1

Using alumina Z1 without hydrothermal treatment as a carrier, the reference catalyst DC1 was prepared by the active component loading method in Example 3. Calculated by oxide and based on the load on the surface of the unit carrier, an X-ray fluorescence spectrometer is used to measure the content of molybdenum oxide and nickel oxide in the catalyst DC1, and an X-ray powder diffractometer is used to measure whether there is molybdenum trioxide in the catalyst DC1. The results are shown in Table 2, and the XRD spectrum of the catalyst DC1 is shown in FIG. 2 .

Comparative example 2

Using alumina Z2 without hydrothermal treatment as a carrier, the reference catalyst DC2 was prepared by the active component loading method in Example 6. Calculated by oxide and based on the load on the surface of the unit carrier, the content of molybdenum oxide and cobalt oxide in the catalyst DC2 was measured by X-ray fluorescence spectrometer, and whether molybdenum trioxide was formed in the catalyst by X-ray powder diffractometer. The measurement results As shown in table 2.

Comparative example 3

Weigh 100g of the Z1 carrier and place it in a tube furnace, blow air into the furnace at an air volume of 100ml/min, pump deionized water into the furnace at a rate of 120ml/hour, and raise the temperature to 500°C at a rate of 2°C/min. The carrier was subjected to steam treatment at 500°C for 3 hours to obtain an alumina carrier DZ1.

Using steam-treated alumina DZ1 as a carrier, the reference catalyst DC3 was prepared by the active component loading method of Example 3. Calculated by oxides and based on the load on the surface of the carrier that has not been treated with water vapor, use X-ray fluorescence spectrometer to measure the content of molybdenum oxide and nickel oxide in catalyst DC3, and use X-ray powder diffractometry to determine whether there is trioxide in the catalyst. Molybdenum formed aggregates, and the measurement results are shown in Table 2.

Examples 7-10 provide the heavy oil hydrotreating method of the present invention and illustrate the heavy oil hydrotreating performance of the heavy oil hydrotreating catalyst provided by the present invention.

Catalysts were evaluated in a 100ml small fixed-bed reactor using atmospheric residual oil with a nickel content of 12ppm, a vanadium content of 18ppm, a sulfur content of 3.2%, a carbon residue of 11%, and a nitrogen content of 0.3%.

Catalysts C1, C2, C3 and C4 were respectively crushed into particles with a diameter of 0.8-1.2 mm, and the catalyst loading was 100 ml. The reaction conditions are as follows: reaction temperature is 380°C, hydrogen partial pressure is 14 MPa, liquid hourly space velocity is 0.6 h ^-1 , hydrogen-oil volume ratio is 1000, and samples are taken after 200 hours of reaction, and the inductively coupled plasma emission spectrometer (ICP- AES) to determine the content of nickel and vanadium in the treated oil. (The instrument used is the PE-5300 plasma light meter of the American PE company, and the specific method is shown in the petrochemical analysis method RIPP124-90).

Use the coulometric method to determine the sulfur content (see the petrochemical analysis method RIPP62-90 for the specific method).

Nitrogen content was determined by coulometric method (see Petrochemical Analysis Method RIPP63-90 for specific methods).

Determination of residual carbon content using micro-method (specific method see petrochemical analysis method RIPP148-90).

Calculate the removal rates of sulfur, residual carbon, nitrogen and metals respectively according to the following formulas:

Comparative example 4-6

The impurity removal performance of the catalysts DC1, DC2 and DC3 was evaluated according to the method of Examples 7-10, and the results are shown in Table 3.

As can be seen from the results in Table 3, when the catalyst provided by the present invention is used for the hydrotreating reaction of heavy oil, the overall impurity removal activity of heavy oil is significantly improved compared with the prior art, especially in the aspects of desulfurization, carbon residue removal and nitrogen removal. .

Table 1

Example number Example 1 Example 2 carrier number Z1 Z2 Specific surface ( ^m2 /g) 248 270 Pore volume (ml/g) 0.66 0.70 Pore diameter(nm) 8 9 Boron oxide (%) 2.1 3.1 Strength (N/mm) 18 17

Table 2

table 3

Claims (12)

1. A heavy oil hydrotreating catalyst, the catalyst comprises boron-containing shaped alumina carrier, metal component molybdenum and metal component cobalt or nickel; in terms of oxides and with the total weight of the boron-containing shaped alumina carrier Based on the basis, the content of boron in the boron-containing shaped alumina carrier is 0.5-5% by weight; calculated as oxide and based on the load on the surface of the unit carrier, the content of molybdenum in the catalyst is 4.8 μmol /m ² -9.0μmol/m ² , the content of the metal component cobalt or nickel is 1.5μmol/m ² -4.0μmol/m ² ; when the catalyst is characterized by XRD, the diffraction angle 2θ=26°±2 ° no MoO ₃ characteristic peaks appear; The boron-containing shaped alumina carrier undergoes hydrothermal treatment under airtight conditions before loading the metal component molybdenum and the metal component cobalt or nickel; The boron-containing shaped alumina carrier that has undergone the hydrothermal treatment is dried before being loaded with the metal component molybdenum and the metal component cobalt or nickel; the temperature of the drying treatment is 60- 350°C, the drying time is 1-48 hours. 2. The catalyst according to claim 1, wherein, in terms of oxides and based on the load on the surface of the unit carrier, the content of the metal component molybdenum in the catalyst is 5.4 μmol/m ² -8.0 μmol/m ² , The content of the metal component cobalt or nickel is 1.8 μmol/m ² -3.6 μmol/m ² . 3. The catalyst according to claim 1, wherein, in terms of oxides and based on the load on the surface of a unit carrier, the content of the metal component molybdenum in the catalyst is 5.9 μmol/m ² -7.5 μmol/m ² , The content of the metal component cobalt or nickel is 2.0 μmol/m ² -3.1 μmol/m ² . 4. The catalyst according to claim 1, wherein the temperature of the hydrothermal treatment is 60-180° C., and the time is 1-24 hours; by weight, the amount of water in the hydrothermal treatment is the weight of boron-containing shaped alumina carrier 100-300% by weight. 5. The catalyst according to claim 1, wherein, the preparation step of the boron-containing shaped alumina support comprises: introducing a boron-containing compound into the precursor of alumina, and then introducing the boron-containing compound into the alumina The precursor is shaped, and the shaped alumina precursor is fired. 6. The catalyst according to claim 1, wherein the boron-containing shaped alumina support has at least one crystal phase selected from the group consisting of γ-, η-, θ-, δ- and χ-alumina crystal phases. 7. The catalyst according to claim 1, wherein the boron-containing shaped alumina carrier is in at least one shape selected from the group consisting of spherical, cylindrical, annular, cloverleaf, quatrefoil, honeycomb and butterfly. 8. The catalyst according to claim 1, wherein the metal component molybdenum and the metal component cobalt or nickel are supported on the boron-containing shaped alumina support by impregnation. 9. The catalyst according to claim 8, wherein the impregnated boron-containing shaped alumina support is subjected to drying treatment and calcination treatment or no calcination treatment; the temperature of the drying treatment is 60-150° C., and the drying treatment time is 1-5 hours; the temperature of the roasting treatment is 350-550° C., and the time of the roasting treatment is 1-6 hours. 10. A heavy oil hydrotreating method, the method comprising: under heavy oil hydrotreating conditions, heavy oil is contacted with the heavy oil hydrotreating catalyst according to any one of claims 1-9 and heavy oil hydrotreating is carried out. 11. The method according to claim 10, wherein the heavy oil is at least one selected from crude oil, atmospheric residual oil, vacuum residual oil, deep waxed oil, light deasphalted oil and coker waxed oil. 12. The method according to claim 10, wherein the heavy oil hydrotreating conditions include: a reaction temperature of 300-550° C., a hydrogen partial pressure of 4-20 MPa, a liquid hourly space velocity of 0.1-3 hours ⁻¹ , and a hydrogen The oil volume ratio is 200-2500.