CN112742406A

CN112742406A - Heavy oil hydrogenation catalyst and preparation method thereof

Info

Publication number: CN112742406A
Application number: CN201911037157.0A
Authority: CN
Inventors: 金浩; 朱慧红; 杨光; 吕振辉; 刘璐; 杨涛
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2019-10-29
Filing date: 2019-10-29
Publication date: 2021-05-04

Abstract

The invention discloses a heavy oil hydrogenation catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: mixing an alumina carrier and a carbon source precursor for reaction, drying a solid-phase material obtained by separating reaction effluent, roasting the dried material in an oxygen-containing atmosphere to obtain a carbon-containing alumina carrier, further loading metal, drying and roasting to obtain the hydrogenation catalyst. The preparation method of the catalyst can improve the uniform dispersion degree of the active metal components on the carrier, so that the active metal in the catalyst is easier to vulcanize, the stability of the catalyst is maintained, and the hydrogenation activity of the catalyst is improved.

Description

Heavy oil hydrogenation catalyst and preparation method thereof

Technical Field

The invention belongs to the technical field of oil refining chemical industry, relates to a catalyst and a preparation method thereof, and particularly relates to a heavy oil hydrogenation catalyst and a preparation method thereof.

Background

China is the second largest petroleum consumer country in the world at present, the first largest petroleum import country, and the external dependence of the Chinese petroleum import in 2019 is over 70 percent and far over 50 percent of the warning line. With the continuous exploitation of petroleum, the imported petroleum in China is continuously heavy and inferior, and the proportion of heavy oil in the imported petroleum is increased year by year. How to realize the full utilization of the heavy oil is the key for solving the energy problem and improving the energy utilization efficiency. At present, heavy oil treatment technologies mainly comprise a heavy oil hydrogenation technology and a delayed coking technology, wherein the hydrogenation technology has higher economic benefit. The heavy oil hydrogenation technologies which are industrialized at present mainly comprise fixed bed hydrogenation technologies and ebullated bed hydrogenation technologies. With the gradual improvement of fuel standards and the gradual strictness of environmental emission, higher requirements are put forward on both hydrogenation technologies, and the improvement of the activity of the catalyst is the key to achieve the aim.

CN104096584A discloses a residual oil hydrogenation catalyst and a preparation method thereof. The catalyst uses a kneaded body of alumina and activated carbon as a carrier, and Ni₂P、MoO₃And/or WO₃CoO and/or NiO are/is used as active components. A small amount of active carbon is introduced into the alumina, so that the Ni content is reduced₂The P active component reacts with the alumina in the generation process, and the dispersity of the P active component is improved, so that the impurity capacities of the catalyst, such as desulfurization, carbon residue and the like, are improved. But the active carbon in the preparation method only reduces Ni₂P interacts with the carrier, and the strong acid part of the alumina is easy to generate coke in the reaction process, so that the long-period stability of the catalyst is influenced.

CN103785400A discloses a preparation method of a high-activity residual oil hydrodemetallization catalyst. The method comprises the steps of firstly carrying out hydrothermal carbonization treatment on an alumina carrier, loading active components Mo and Ni after drying, then roasting in a nitrogen atmosphere, and then roasting in an air atmosphere to finally obtain the catalyst. After the alumina carrier is carbonized, a layer of carbon deposit is generated on the surface, so that the active components and the carrier have weaker action and are distributed more uniformly on the carrier, and the active components are easy to be completely vulcanized, thereby obviously improving the demetalization and desulfurization activities of the catalyst. However, the catalyst prepared by the method has weak action of active components and a carrier, and directly influences the long-period stability of the catalyst.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a heavy oil hydrogenation catalyst and a preparation method thereof. The preparation method of the catalyst weakens the strong acidity of the alumina carrier by properly depositing carbon on the alumina carrier, properly reduces the interaction between the alumina and the hydrogenation active metal component, improves the uniform dispersion degree of the active metal component on the carrier, ensures that the active metal in the catalyst is easier to vulcanize, maintains the stability of the catalyst and improves the hydrogenation activity of the catalyst.

The invention provides a preparation method of a heavy oil hydrogenation catalyst, which comprises the following steps:

(1) adding an alumina carrier into a reactor, and then adding a carbon source precursor to react at 100-400 ℃;

(2) drying the solid-phase material obtained by separating the reaction effluent obtained in the step (1);

(3) roasting the dried material obtained in the step (2) in an oxygen-containing atmosphere to obtain a carbon-containing alumina carrier;

(4) mixing a compound containing a hydrogenation metal component with ammonia water to obtain a solution A;

(5) and (4) mixing the solution A obtained in the step (4) with the carbon-containing alumina carrier obtained in the step (3), uniformly mixing, drying and roasting to obtain the hydrogenation catalyst.

In the preparation method of the heavy oil hydrogenation catalyst, the carbon source precursor in the step (1) can be one or more of gasoline, diesel oil, alkane with 6-20 carbon atoms, olefin and aromatic hydrocarbon.

In the preparation method of the heavy oil hydrogenation catalyst, the volume ratio of the carbon source precursor to the alumina carrier in the step (1) is 2: 1-20: 1.

In the preparation method of the heavy oil hydrogenation catalyst, the reaction time in the step (1) is 1-5 hours.

In the preparation method of the heavy oil hydrogenation catalyst, the drying temperature in the step (2) is 70-120 ℃, and the drying time is 8-24 hours.

In the preparation method of the heavy oil hydrogenation catalyst, the oxygen-containing gas in the step (3) is one or more of oxygen, air, oxygen and nitrogen, and mixed gas of oxygen and inert gas.

In the preparation method of the heavy oil hydrogenation catalyst, the roasting temperature in the step (3) is 250-500 ℃, and the roasting time is 4-12 hours.

In the preparation method of the heavy oil hydrogenation catalyst, the compound containing the hydrogenation metal component in the step (4) is a compound containing a group VIB metal and/or a group VIII metal, the compound containing the group VIB metal may be one or more of a molybdenum-containing compound and a tungsten-containing compound, and the compound containing the group VIII metal is one or more of a nickel-containing compound and a cobalt-containing compound. The molybdenum-containing compound may be ammonium heptamolybdate and/or ammonium tetramolybdate, preferably ammonium heptamolybdate; the tungsten-containing compound is ammonium metatungstate; the nickel-containing compound is basic cobalt carbonate; the cobalt-containing compound is basic cobalt carbonate.

In the above method for preparing a heavy oil hydrogenation catalyst, the compound containing a hydrogenation metal component in step (4) is preferably a molybdenum-containing compound and a nickel-containing compound, and the molybdenum-containing compound may be ammonium heptamolybdate and/or ammonium tetramolybdate, preferably ammonium heptamolybdate; the nickel-containing compound is basic nickel carbonate.

In the preparation method of the heavy oil hydrogenation catalyst, the ammonia water concentration in the step (4) is 15-25 wt%.

In the above method for preparing a heavy oil hydrogenation catalyst, the drying conditions in step (5) include: the drying temperature is 90-120 ℃, and the drying time is 1-12 h.

In the preparation method of the heavy oil hydrogenation catalyst, the roasting in the step (5) is carried out in an inert atmosphere or a nitrogen atmosphere, the inert gas is one or more of helium, neon, argon, krypton and xenon, the roasting temperature is 400-600 ℃, and the roasting time is 1-5 hours.

The second aspect of the invention provides a heavy oil hydrogenation catalyst obtained by the preparation method, the catalyst comprises a hydrogenation active metal component and a carrier, the hydrogenation active metal component is one or more of VIB group metals and/or VIII group metals, and the carrier is alumina.

In the heavy oil hydrogenation catalyst, the VIB group metal is Mo and/or W, and the VIII group metal is Ni and/or Co.

In the heavy oil hydrogenation catalyst, the concentration of the compound containing hydrogenation active metals in the solution and the dosage of the solution are such that the content of the metal component of the VIB group in the final catalyst is 5-25 wt%; the content of the VIII group metal component is 1wt% -10 wt%.

In the heavy oil hydrogenation catalyst, the hydrogenation metal component is more preferably Mo, Ni, or Co.

In the heavy oil hydrogenation catalyst, other metals, such as one or more of Zr, Ti, B, La and Ce, can be introduced into the catalyst carrier.

In the heavy oil hydrogenation catalyst, the properties of the heavy oil hydrogenation catalyst are as follows: the specific surface area is 160-270 m²The pore volume is 0.50-0.75 mL/g.

Compared with the prior art, the heavy oil hydrogenation catalyst and the preparation method thereof have the following advantages:

in the preparation method of the heavy oil hydrogenation catalyst, carbon deposition is ensured to be generated on an acid site of alumina by the reaction of a carbon source precursor on the alumina carrier and by controlling reaction conditions, and the carbon deposition on a weak acid site in the alumina carrier is removed and the carbon deposition on a strong acid site is reserved by regulating roasting conditions, so that the carbon-containing alumina carrier prepared by the method has the following advantages: on one hand, the weakening of strong acid sites of the alumina carrier is beneficial to improving the dispersion of active metals in an active metal solution (molybdenum nickel ammonium solution) on the carrier, and simultaneously, the strong interaction of the active metals and the alumina carrier is properly weakened, so that the active metals on the catalyst are easier to vulcanize, the stability of the catalyst is ensured, and the hydrogenation activity of the catalyst is improved; on the other hand, the weakening of strong acid sites of the alumina carrier reduces carbon deposition of the catalyst in the reaction process, improves the long-period stability of the catalyst, and solves the problems of short service period and poor stability of the current heavy oil hydrogenation catalyst.

Drawings

FIG. 1 shows temperature programmed reduction (H) of example 1 of the present invention and comparative example 1₂TPR) spectrum.

Detailed Description

The embodiments and effects of the present invention will be further described below with reference to the accompanying drawings. In the present invention, wt% is a mass fraction.

The specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen physical adsorption method, and are particularly measured by adopting a low-temperature nitrogen adsorption instrument of American Mike company ASAP2420 model; the specific process comprises the following steps: and (3) carrying out vacuum treatment on a small amount of sample at 300 ℃ for 3-4 h, and finally placing the product under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen absorption-desorption test. Wherein the surface area is obtained according to a BET equation, and the pore size distribution is obtained according to a BJH model. The acidity of the catalyst was measured by chemical adsorption (pyridine) and infrared spectroscopy using a T-IR550 model infrared spectrometer from Nicolet, USA. Catalyst temperature programmed reduction (H)₂TPR) was measured using an Auto chem model 2920 chemisorption instrument from Mike. The degree of dispersion of the active metal on the catalyst was determined by means of a MultiLab 2000X-ray photoelectron spectrometer from Thermo corporation, USA.

Example 1

(1) Preparation of the support

100mL of alumina carrier (prepared by kneading, molding and roasting commercial pseudo-boehmite powder, 0.3-0.7 mm of spherical particles with the specific surface area of 292 m)²/g, pore volume of 0.782 mL/g) is added into a reactor, then 1000mL of n-decane solution is added, the reaction is carried out for 3h at 320 ℃, then the solid phase material obtained by separating the reaction effluent is dried for 12h at 110 ℃, and the dried material is put into the air atmosphereAnd roasting at 400 ℃ for 8h to prepare the carbon-containing alumina carrier.

(2) Catalyst preparation

Dissolving 7.22g of ammonium heptamolybdate and 2.65g of basic nickel carbonate in an ammonia water solution with the concentration of 20wt%, and filtering to obtain 50mL of constant volume to obtain the Mo-Ni ammonia water solution.

Adding Mo-Ni ammonia water solution into 50g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h, and roasting at 500 ℃ for 3h under nitrogen atmosphere to obtain the catalyst, wherein MoO is₃The content was 10.0wt%, the NiO content was 2.5wt%, and the carbon content was 5.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.

(3) Catalyst evaluation

The catalyst is subjected to activity evaluation on a Continuous Stirred Tank Reactor (CSTR), the catalyst is filled to 100mL, the CSTR has good full back-mixing performance, and similar to a boiling bed Reactor, the CSTR can be used for replacing the boiling bed Reactor to evaluate the performance of the catalyst. The properties and evaluation conditions of the raw oil are shown in Table 2. The results of the evaluation of the catalyst activity for an operating time of 500 hours are shown in Table 3.

Example 2

(1) Preparation of the support

100mL of alumina carrier (prepared by kneading, molding and roasting commercial pseudo-boehmite powder, 0.3-0.7 mm of spherical particles with the specific surface area of 280 m²/g, the pore volume is 0.782 mL/g) is added into a reactor, then 800mL of n-dodecene solution is added, the reaction is carried out for 3h at 300 ℃, then the solid phase material obtained by separating the reaction effluent is dried for 12h at 110 ℃, and the dried material is roasted for 8h at 380 ℃ in the air atmosphere, thus obtaining the carbon-containing alumina carrier.

(2) Catalyst preparation

Dissolving 11.71g of ammonium heptamolybdate and 4.33g of basic nickel carbonate in an ammonia water solution with the concentration of 20wt%, and filtering to obtain 50mL of constant volume to obtain the Mo-Ni ammonia water solution.

Adding Mo-Ni ammonia water solution into 50g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h, and roasting at 500 ℃ for 3h under nitrogen atmosphere to obtain the catalyst, wherein MoO is₃The content was 15.0wt%, the NiO content was 3.8wt%, and the carbon content was 4.8 wt%. The physicochemical properties of the catalyst are shown in Table 1.

(3) Catalyst evaluation

The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 3.

Example 3

(1) Preparation of the support

100mL of alumina carrier (prepared by kneading, molding and roasting commercial pseudo-boehmite powder, 0.3-0.7 mm of spherical particles with specific surface area of 290 m²/g, the pore volume is 0.782 mL/g) is added into a reactor, then 1200mL of n-hexadecane solution is added, the reaction is carried out for 3h at 360 ℃, then the solid phase material obtained by separating the reaction effluent is dried for 12h at 110 ℃, and the dried material is roasted for 8h at 450 ℃ in the air atmosphere to obtain the carbon-containing alumina carrier, wherein.

(2) Catalyst preparation

16.90g of ammonium heptamolybdate and 6.18g of basic nickel carbonate are dissolved in an ammonia water solution with the concentration of 20wt%, and the volume is 50mL after filtration, thus obtaining the Mo-Ni ammonia water solution.

Adding Mo-Ni ammonia water solution into 50g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h, and roasting at 500 ℃ for 3h under nitrogen atmosphere to obtain the catalyst, wherein MoO is₃The content is 20.0wt%, the NiO content is 5.0wt%, and the carbon content is 4.0 wt%. The physicochemical properties of the catalyst are shown in Table 1.

(3) Catalyst evaluation

Example 4

In example 1, the amount of ammonium heptamolybdate was changed to 11.71g and the amount of basic nickel carbonate was changed to 4.33g, and the remainder was the same as in example 1, to obtain a catalyst in which MoO was present₃The content was 15.0wt%, the NiO content was 3.8wt%, and the carbon content was 5.1 wt%. The physicochemical properties of the catalyst are shown in Table 1.

Example 5

In example 1, 16.90g of ammonium heptamolybdate and 6.18g of basic nickel carbonate were used instead, whichThe same procedure as in example 1 was followed to obtain a catalyst in which MoO was present₃The content was 20.0wt%, the NiO content was 5.0wt%, and the carbon content was 4.7 wt%. The physicochemical properties of the catalyst are shown in Table 1.

Example 6

A catalyst was prepared as in example 1 except that in example 1, the basic nickel carbonate was changed to 2.60g of basic cobalt carbonate. MoO in catalyst₃The content was 10.0wt%, the CoO content was 2.5wt%, and the carbon content was 5.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.

Example 7

A catalyst was prepared according to example 1, and a long-term stability evaluation test was conducted for 1000 hours under the evaluation conditions of example 1, and the evaluation results are shown in Table 3.

Comparative example 1

In example 1, the Mo — Ni ammonia aqueous solution was completely added to 50g of alumina carrier, mixed uniformly, left to stand for 3 hours, then dried at 110 ℃ for 4 hours, and calcined at 500 ℃ for 3 hours under nitrogen atmosphere to obtain a catalyst, wherein MoO is the catalyst₃The content was 10.0wt%, and the NiO content was 2.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.

Comparative example 2

Compared with the embodiment 1, the dried carrier is directly soaked in the active metal solution without roasting in the air atmosphere, the roasting in the nitrogen atmosphere is changed into the roasting in the air atmosphere, and the rest is the same as the embodiment 1, so that the catalyst is obtained, wherein MoO is contained in the catalyst₃The content was 10.0wt%, and the NiO content was 2.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.

Comparative example 3

A catalyst was prepared according to comparative example 2, and a long-term stability evaluation test was conducted for 1000 hours under the evaluation conditions of example 1, and the evaluation results are shown in Table 3.

TABLE 1 physicochemical Properties of the catalyst

TABLE 2 Properties and evaluation conditions of the stock oils

TABLE 3 evaluation results of catalysts

The results of the evaluation of the activity of comparative example 1 are shown in Table 3, where the activity is 100.

In table 3, HDS stands for hydrodesulfurization, HDCCR for hydrodecarbon residue, and HDM for hydrodemetallization.

As can be seen from table 3: the hydrogenation activity of the catalyst prepared by the research is greatly improved compared with that of the catalyst prepared by a comparative example, because the action of the active metal and the carrier of the catalyst prepared by the research is weakened, the reduction temperature of the catalyst is lower, the catalyst can be better dispersed, and the utilization rate of the active metal is improved, as shown in table 4 and figure 1. The catalyst prepared by the research is particularly suitable for the boiling bed hydrogenation reaction of heavy oil or residue oil.

TABLE 4 degree of dispersion of active metals on catalyst

Wherein I_Mo/I_AlRepresents the dispersion of the active metal Mo on the alumina; i is_Ni/I_AlIndicating the dispersion of the active metal Ni on the alumina.

Claims

1. A preparation method of a heavy oil hydrogenation catalyst comprises the following steps:

2. A process for producing a heavy oil hydrogenation catalyst as set forth in claim 1, wherein: in the step (1), the carbon source precursor is one or more of gasoline, diesel oil, alkane with carbon number of 6-20, olefin and aromatic hydrocarbon.

3. A process for producing a heavy oil hydrogenation catalyst as set forth in claim 1, wherein: the volume ratio of the carbon source precursor to the alumina carrier in the step (1) is 2: 1-20: 1.

4. A process for producing a heavy oil hydrogenation catalyst as set forth in claim 1, wherein: in the step (2), the drying temperature is 70-120 ℃, and the drying time is 8-24 h.

5. A process for producing a heavy oil hydrogenation catalyst as set forth in claim 1, wherein: in the step (3), the oxygen-containing gas is one or more of oxygen, air, oxygen and nitrogen, and mixed gas of oxygen and inert gas.

6. A process for producing a heavy oil hydrogenation catalyst as set forth in claim 1, wherein: in the step (3), the roasting temperature is 250-500 ℃, and the roasting time is 4-12 h.

7. A process for producing a heavy oil hydrogenation catalyst as set forth in claim 1, wherein: the compound containing the hydrogenation metal component in the step (4) is a compound containing VIB group metal and/or VIII group metal.

8. A process for producing a heavy oil hydrogenation catalyst as set forth in claim 1, wherein: the concentration of the ammonia water in the step (4) is 15wt% -25 wt%.

9. A process for producing a heavy oil hydrogenation catalyst as set forth in claim 1, wherein: the drying conditions in step (5) include: the drying temperature is 90-120 ℃, and the drying time is 1-12 h.

10. A process for producing a heavy oil hydrogenation catalyst as set forth in claim 1, wherein: and (5) roasting in an inert atmosphere or a nitrogen atmosphere, wherein the inert gas is one or more of helium, neon, argon, krypton and xenon, the roasting temperature is 400-600 ℃, and the roasting time is 1-5 hours.

11. A heavy oil hydrogenation catalyst, characterized by: the heavy oil hydrogenation catalyst is prepared by the method of any one of claims 1 to 10.

12. A heavy oil hydrogenation catalyst as set forth in claim 11, wherein: the properties of the heavy oil hydrogenation catalyst are as follows: the specific surface area is 160-270 m²The pore volume is 0.50-0.75 mL/g.