CN113559868B

CN113559868B - Heavy oil hydrogenation catalyst and preparation method and application thereof

Info

Publication number: CN113559868B
Application number: CN202010348638.XA
Authority: CN
Inventors: 胡大为; 王振; 杨清河; 孙淑玲; 韩伟; 户安鹏; 邓中活
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-04-28
Filing date: 2020-04-28
Publication date: 2023-04-07
Anticipated expiration: 2040-04-28
Also published as: CN113559868A

Abstract

The invention provides a heavy oil hydrogenation catalyst and a preparation method and application thereof, the heavy oil hydrogenation catalyst comprises a carrier and an active component loaded on the carrier, the carrier comprises inorganic heat-resistant oxide, nickel oxide and a compound thereof, wherein the absorbances at 630nm and 500nm of the carrier are respectively F when the carrier is measured by diffuse reflection ultraviolet visible spectrum ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ 1.3 to 3.0; the active component comprises at least one VIB group metal, and the content of the active component is 8-30 percent by taking the total weight of the catalyst as the reference; in the Raman spectrum of the heavy oil hydrogenation catalyst, the Raman spectrum is positioned at 940cm ^‑1 Intensity of nearby characteristic peak and intensity of 840cm ^‑1 The intensities of the near characteristic peaks are respectively I ₉₄₀ And I ₈₄₀ And the ratio of the two K = I ₉₄₀ /I ₈₄₀ Is 1.0 to 2.4. The heavy oil hydrogenation catalyst provided by the invention has excellent stability while ensuring good initial activity, greatly prolongs the service life of the heavy oil hydrogenation catalyst, improves the production efficiency, and has good application prospects.

Description

Heavy oil hydrogenation catalyst and preparation method and application thereof

Technical Field

The invention relates to the field of catalysts, and particularly relates to a heavy oil hydrogenation catalyst, and a preparation method and application thereof.

Background

The heavy oil processing, especially the deep processing of the residual oil, is not only beneficial to improving the utilization rate of the crude oil and relieving the tension trend of energy supply, but also can reduce the environmental pollution and realize the high-efficiency clean utilization of energy.

For heavy raw oil, after being pretreated by a hydrogenation process, secondary processing is carried out, so that the yield of light oil can be improved, and the content of pollutants such as sulfur, nitrogen and the like in the oil can be reduced, therefore, the demand of the market on the light oil is continuously increased, and the environmental protection regulations tend to be strict today, and the heavy raw oil is generally favored by oil refining manufacturers. Compared with light oil products, heavy oil contains a large amount of impurities such as sulfur, nitrogen, metal and the like, and contains easily coking species such as asphaltene and the like, so that the heavy oil has higher requirements on the activity and the stability of the catalyst. The deactivation of the heavy oil hydrogenation catalyst is caused by two factors, namely, the deposition of metal to destroy the original active phase structure of the catalyst, and carbon deposits on the surface of the active phase to cover the active center, so that the reaction performance of the catalyst is reduced. Therefore, how to improve the stability of the active phase structure of the catalyst and reduce the damage, aggregation and poisoning of the active phase structure of the catalyst in the reaction process is a key technology for improving the activity stability of the catalyst.

CN107583659A discloses a gasoline selective hydrodesulfurization catalyst, which is a composite alumina carrier containing zinc aluminum spinel prepared by a non-constant pH alternative titration method, wherein the catalyst prepared after loading cobalt and molybdenum has good selectivity and reaction stability in the gasoline hydrodesulfurization process.

Compared with distillate oil, the heavy oil hydrogenation catalyst needs higher reaction activity and has higher requirement on activity stability, and the prior art which is not disclosed can well meet the requirements of both the activity and the stability of the catalyst, thereby seriously influencing the actual industrial application effect of the catalyst.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

A primary object of the present invention is to overcome at least one of the above-mentioned drawbacks of the prior art, and to provide a heavy oil hydrogenation catalyst, a preparation method and an application thereof, so as to solve the problem that the activity and stability of the existing heavy oil hydrogenation catalyst are difficult to be considered.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a heavy oil hydrogenation catalyst, which comprises: the carrier comprises inorganic heat-resistant oxide, nickel oxide and a compound thereof, wherein the absorbances at 630nm and 500nm of the carrier are respectively F when the carrier is measured by diffuse reflection ultraviolet visible spectrum ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ 1.3 to 3.0; the active component comprises at least one VIB group metal, and the content of the active component is 8-30 percent by weight calculated by oxides and based on the total weight of the heavy oil hydrogenation catalyst; in the Raman spectrum of the heavy oil hydrogenation catalyst, the Raman spectrum is 940cm ^-1 Intensity of nearby characteristic peak and intensity of 840cm ^-1 The intensities of the near characteristic peaks are respectively I ₉₄₀ And I ₈₄₀ And the ratio of the two K = I ₉₄₀ /I ₈₄₀ Is 1.0 to 2.4.

According to one embodiment of the invention, the inorganic refractory oxide is alumina and the composite is a nickel aluminate spinel.

According to one embodiment of the present invention, the nickel content is 1% to 8% by weight on an oxide basis and based on the total weight of the heavy oil hydrogenation catalyst.

According to one embodiment of the invention, the active component further comprises one or more of a group VIII metal.

According to one embodiment of the present invention, when the group VIII metal is nickel, the content of the group VIII metal is 0.1% to 3% by oxide and the total content of nickel in the catalyst is not more than 8%.

According to one embodiment of the invention, the carrier further comprises an adjuvant selected from metallic adjuvants and/or non-metallic adjuvants.

According to one embodiment of the invention, the promoter is a metal promoter, and the content of the metal promoter is 0.1-3% calculated by elements and based on the total weight of the heavy oil hydrogenation catalyst.

According to one embodiment of the invention, the additive is a non-metal additive, and the content of the non-metal additive is 0.5-15% calculated by elements and based on the total weight of the heavy oil hydrogenation catalyst.

According to one embodiment of the invention, the at least one group VIB metal is molybdenum and/or tungsten.

The invention also provides a preparation method of the heavy oil hydrogenation catalyst, which comprises the following steps: mixing an inorganic heat-resistant oxide precursor, a nickel source and a forming auxiliary agent to obtain a mixture, and forming; roasting the formed product at 600-800 deg.c for 1-10 hr to obtain carrier; and dipping the carrier in a solution containing active components, drying the dipped product, and activating at the temperature of 300-550 ℃ to obtain the heavy oil hydrogenation catalyst.

According to one embodiment of the invention, the temperature of the calcination is 650 ℃ to 730 ℃.

According to one embodiment of the present invention, the temperature rise rate of the firing is 50 ℃/hr to 600 ℃/hr.

According to one embodiment of the invention, the inorganic refractory oxide precursor is pseudo-boehmite, and the nickel source is selected from one or more of nickel nitrate, nickel sulfate and basic nickel carbonate; the solution containing the active component is an aqueous solution comprising at least one group VIB metal oxide or salt selected from one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, tungsten oxide, ammonium tungstate and ammonium paratungstate.

According to an embodiment of the present invention, before the forming process, the forming process further comprises adding an assistant precursor to the mixture, so that the catalyst carrier contains an assistant selected from a metal assistant and/or a non-metal assistant.

According to one embodiment of the present invention, the forming aid comprises a peptizing agent selected from one or more of aqueous nitric acid, aqueous hydrochloric acid and aqueous citric acid, and a lubricant selected from one or more of sesbania powder, citric acid, starch and carboxymethyl cellulose.

According to one embodiment of the invention, the forming process comprises: kneading the mixture to obtain a plastic body; drying the plastic body after molding to obtain a molded product; wherein the shaping method is selected from one or more of extruding, rolling ball, tabletting and granulating.

According to one embodiment of the invention, the drying temperature is 100-250 ℃ and the drying time is 1-6 h.

The invention also provides the application of the heavy oil hydrogenation catalyst in heavy oil hydrogenation reaction.

According to the technical scheme, the invention has the beneficial effects that:

according to the heavy oil hydrogenation catalyst provided by the invention, the carrier containing the spinel structure is adopted, the hydrogenation active component is loaded on the carrier, and the stability of the heavy oil hydrogenation catalyst is greatly improved while the good initial activity is ensured through a specific process, so that the service life of the heavy oil hydrogenation catalyst is prolonged, the production efficiency is improved, and the heavy oil hydrogenation catalyst has a good application prospect.

Detailed Description

The following presents various embodiments, or examples, in order to enable one of ordinary skill in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.

The invention provides a heavy oil hydrogenation catalyst, which comprises: a carrier and a carrier supported on the sameActive components on a carrier, wherein the carrier comprises inorganic heat-resistant oxide, nickel oxide and a compound thereof, and the absorbances of the carrier at 630nm and 500nm are respectively F when the carrier is measured by diffuse reflection ultraviolet visible spectrum ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ 1.3 to 3.0; the active component comprises at least one VIB group metal, and the content of the active component is 8-30 percent by taking the total weight of the catalyst as the reference; wherein, the Raman spectrum of the catalyst is 940cm ^-1 Intensity of nearby characteristic peak and intensity of 840cm ^-1 The intensities of the near characteristic peaks are respectively I ₉₄₀ And I ₈₄₀ And the ratio of the two K = I ₉₄₀ /I ₈₄₀ Is 1.0 to 2.4.

In the field of catalysis, it is generally accepted that the formation of spinel structures generally affects the initial activity of the catalyst. However, the inventors of the present invention have found that, although the formation of the spinel structure affects the initial activity of the catalyst, the formation of the spinel structure in a proper amount does not have a great influence on the overall activity of the catalyst, and the spinel structure formed gradually releases the reactivity as the catalyst participates in the extension of the reaction process.

Furthermore, the invention also finds that the activity of other active components can be influenced in the process of forming the spinel structure, and if the catalyst carrier contains the spinel structure, the carrier can be used as a functional carrier, so that the flexibility of subsequent loading of the active components is further improved, the application range of the catalyst is enlarged, and the activity of other components is not influenced in the process of forming the spinel structure.

Tests have shown that a catalyst which has a good initial activity and a good stability of the activity, i.e. a catalyst according to the invention which is characterized by the above-mentioned parameters, has an initial activity when the aforementioned ratio Q, which represents the content of spinel structure in the support, is between 1.3 and 3.0High sexual activity and good stability. Preferably, the aforementioned ratio Q is 1.4 to 2.8. When the Q value is less than 1.3, the improvement of the activity stability is not obvious; when the Q value is more than 3.0, the initial activity is too low, which affects the normal use of the catalyst. Meanwhile, in the Raman spectrum of the catalyst, the Raman spectrum is positioned at 940cm ^-1 Intensity of nearby characteristic peak and intensity of 840cm ^-1 The intensities of the near characteristic peaks are respectively I ₉₄₀ And I ₈₄₀ And the ratio of the two K = I ₉₄₀ /I ₈₄₀ When the amount is 1.0 to 2.4, the reaction force between the active component supported on the carrier and the carrier in the catalyst is weak, and the activity is high.

In some embodiments, the inorganic refractory oxide is preferably alumina, and the composite is nickel aluminate spinel. That is, the catalyst support contains alumina, nickel oxide and a nickel aluminate spinel structure. The aforementioned active component is preferably molybdenum (Mo) and/or tungsten (W), more preferably molybdenum.

Further, the active component may further contain one or more of group VIII metals, for example, nickel, cobalt, etc., and when nickel is further added to the active component, the catalyst contains two parts of nickel, one part of nickel in the carrier and one part of nickel in the active component, and the nickel of the active component does not participate in the formation of a spinel structure, and thus, the initial activity of the catalyst can be improved. It should be noted that when the group VIII metal is nickel, the content of the group VIII metal is 0.1% to 3% by oxide and based on the total weight of the heavy oil hydrogenation catalyst, and the total nickel content in the catalyst is not more than 8% to ensure that the overall nickel content in the catalyst is controlled within a proper range.

In some embodiments, the nickel content is 1% to 8%, such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, etc., on an oxide basis and based on the total weight of the heavy oil hydrogenation catalyst. By controlling the content of nickel, the amount of the formed nickel aluminate spinel can be controlled, thereby ensuring that the initial catalytic activity is not too low while the stability of the catalytic activity is improved.

The carrier can further comprise an auxiliary agent, wherein the auxiliary agent can be a metal auxiliary agent and/or a nonmetal auxiliary agent, the metal auxiliary agent is selected from one or more of alkali metals, alkaline earth metals and rare earth metals, such as potassium, sodium, magnesium, lanthanum and the like, and the nonmetal auxiliary agent is selected from one or more of boron and silicon.

When the metal additive is added, the content of the metal additive is 0.1-3% by element and based on the total weight of the heavy oil hydrogenation catalyst. For example, when the carrier contains magnesium, the content of magnesium is 0.4% to 3%, and the content of magnesium can be adjusted to adjust the acidity or basicity of the carrier, thereby reducing the amount of carbon deposition. When the carrier contains lanthanum, the lanthanum content is 0.1-1.5%. By adding a proper amount of lanthanum on the carrier, the growth of carrier grains can be inhibited during high-temperature roasting, the dispersion degree of active components is improved, and further the catalytic activity is improved.

When the non-metal additive is added, the content of the non-metal additive is 0.5 to 15 percent by element and based on the total weight of the heavy oil hydrogenation catalyst. For example, when the carrier contains boron, the content of the boron is 0.5% -5%, and the pore structure of the carrier can be improved by adding the boron, so that the diffusion performance of the carrier is improved. When the carrier contains silicon, the content of the silicon is 3% -15%, the property of the carrier can be adjusted by controlling the content of the silicon in the carrier, and the stability of the catalytic activity is improved.

The heavy oil hydrogenation catalyst of the present invention may further comprise sulfur. Experiments show that when the heavy oil hydrogenation catalyst contains sulfur, the activity and activity stability of the catalyst can be obviously improved. Generally, the sulfur content is 0.5% to 3%, for example, 0.7%, 0.9%, 1.3%, 1.5%, 1.9%, 2.8%, 3%, etc., in terms of element, based on the total weight of the heavy oil hydrogenation catalyst. It should be noted that, one or more of the above-mentioned auxiliaries added to the catalyst may be added, but the total amount of the auxiliaries added does not generally exceed the total content range of the above-mentioned metal auxiliaries or non-metal auxiliaries.

Experiments show that in the preparation method of the invention, the carrier with the spinel structure can be formed only by roasting at the temperature of 600-800 ℃ for 1-10 hours. The roasting temperature is too low or the roasting time is too short, the content of spinel in the obtained carrier is too low, and the activity stability improvement effect is not obvious; if the roasting temperature is too high or the roasting time is too long, the spinel content in the obtained carrier is too high, and the initial activity of the catalyst is influenced.

According to the present invention, the temperature of the calcination is preferably 610 to 780 ℃, more preferably 630 to 750 ℃, and most preferably 650 to 730 ℃, for example 650 ℃, 660 ℃, 680 ℃, 700 ℃, 710 ℃, 720 ℃ or the like. One skilled in the art should be able to select the appropriate firing time according to the firing temperature.

In the present invention, the above-mentioned roasting is a roasting that is conventional in the art, and can be raised from the ambient temperature to the roasting temperature, and the temperature raising rate during roasting can be 50 ℃/hr to 600 ℃/hr, preferably 100 ℃/hr to 550 ℃/hr, for example, 110 ℃/hr, 130 ℃/hr, 150 ℃/hr, 200 ℃/hr, 230 ℃/hr, 350 ℃/hr, 400 ℃/hr, 500 ℃/hr, 520 ℃/hr, and the like.

Meanwhile, according to the present invention, the inventors found that the group VIB metal of the active component, such as molybdenum (Mo), tungsten (W), etc., causes too strong force with the carrier at an excessively high activation temperature, thereby causing a decrease in the activity of the catalyst. Therefore, the spinel structure is formed on the carrier firstly, and then the active component is loaded and activated at a lower temperature, so that the characteristic that the spinel structure provides gradual release of reaction activity can be utilized, the activity stability of the catalyst is improved, the service life of the catalyst is prolonged, and meanwhile, the loaded active component can also contribute to improving the activity of the catalyst, so that the catalyst has excellent performance. In some embodiments, the inorganic refractory oxide precursor is pseudo-boehmite and the nickel source is selected from one or more of nickel nitrate, nickel sulfate, and nickel hydroxycarbonate.

In addition, the present invention also includes the addition of an auxiliary precursor prior to the shaping process to introduce the desired auxiliary. For example, when magnesium is introduced, the magnesium source may be one or more of magnesium oxide, magnesium salt; when boron is introduced, the boron source is one or more of boron trioxide, boric acid and borate; when lanthanum is introduced, the lanthanum source is one or more of lanthanum nitrate and lanthanum salt; when silicon is introduced, the silicon source is one or more of silicon dioxide, silicic acid and silicate; when sulfur is introduced, the sulfur source may be one or more of sulfuric acid, metal sulfates. Of course, one skilled in the art can select other water-soluble salts of these metals or non-metals according to specific circumstances, and the present invention is not particularly limited thereto.

After the raw materials are mixed, a forming aid is added, and the obtained mixture is further subjected to forming treatment. The forming aid generally includes a peptizer and a lubricant, and may also include other substances, and the invention is not limited thereto. Peptizing agents include, but are not limited to, one or more of aqueous nitric acid, aqueous hydrochloric acid, and aqueous citric acid, and lubricants include, but are not limited to, one or more of sesbania powder, citric acid, starch, and carboxymethyl cellulose.

Further, the forming treatment comprises mixing the inorganic heat-resistant oxide precursor, a nickel source, a forming aid and optionally an aid for kneading treatment to obtain a plastic body; and drying the plastic body after molding to obtain a molded product.

Specifically, the shaping method is selected from one or more of extruding, rolling, tabletting and granulating. The catalyst carrier may be formed into various shapes for easy handling, such as spheres, honeycombs, bird nests, tablets or strips (e.g., clover, butterfly, cylindrical, etc.), as required. The adding amount of each raw material meets the content range of each element of the catalyst carrier by taking the total weight of the heavy oil hydrogenation catalyst as a reference; the amount of water and the amount of each forming aid are such that the materials formed by mixing the nickel source, the pseudo-boehmite, each aid and the like can sufficiently meet the requirement of subsequent forming. Sufficient for the subsequent forming needs means that the water/powder ratio in the mixed material is appropriate, as is well known to those skilled in the art.

In some embodiments, the plastic body is dried at 100-250 ℃ after molding, such as 100 ℃, 120 ℃, 135 ℃, 170 ℃, 210 ℃, 230 ℃ and the like, and the drying time is 1-6 h, such as 1h, 2h, 4h, 5h, 6h and the like.

Further, an active component is supported on a carrier forming a spinel structure. Specifically, the carrier is impregnated in a solution containing an active component, and the impregnated product is dried and then activated at 300 to 550 ℃, for example, 300 ℃, 320 ℃, 350 ℃, 370 ℃, 400 ℃, 500 ℃ or the like, to obtain the heavy oil hydrogenation catalyst. Wherein the drying temperature of the impregnated product is 100-150 ℃, such as 100 ℃, 120 ℃, 135 ℃, 140 ℃, 150 ℃ and the like, and the drying time is 1-6 h, such as 1h, 2h, 4h, 5h, 6h and the like. The activation time is 1h to 10h, for example, 1h, 2h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, and the like.

In some embodiments, the aforementioned solution containing an active component is an aqueous solution comprising an oxide or salt of an active component selected from one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, tungsten oxide, ammonium tungstate, and ammonium paratungstate. Of course, the skilled person can also select other water-soluble salts or complex salts of the active ingredient in combination with the specific circumstances, which are not particularly limited.

Alternatively, the aqueous solution containing the oxide or salt of the active ingredient may further contain other ingredients such as ammonia, phosphoric acid, citric acid, or the like to facilitate the introduction of the active ingredient. Wherein, when the other components are phosphorus additives, the adopted phosphorus-containing compound is selected from one or more of phosphoric acid, phosphorous acid, phosphate and phosphite, and phosphoric acid is preferred; when the other component is an organic additive, the organic additive is preferably selected from one or more of oxygen-containing or nitrogen-containing organic compounds, wherein the oxygen-containing organic compound can be one or more of organic alcohol and organic acid, and the nitrogen-containing organic compound can be one or more of organic amine. More specifically, the oxygen-containing organic compound is one or more of ethylene glycol, glycerol, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid, and the nitrogen-containing organic compound is ethylenediamine, EDTA and ammonium salt thereof.

In conclusion, the catalyst has high initial activity and good stability by firstly obtaining the carrier containing the spinel structure and loading the hydrogenation active component on the basis, greatly prolongs the service life of the heavy oil hydrogenation catalyst, improves the production efficiency and has good application prospect.

The following examples further illustrate the invention but should not be construed as limiting it. The reagents used in these examples, except where specifically indicated, were all chemically pure reagents and were commercially available.

In the following examples and comparative examples, the composition of the catalyst was determined by X-ray fluorescence spectroscopy (XRF), as specified in petrochemical analysis method RIPP133-90.

In the following examples and comparative examples, the formation of nickel aluminate spinel structure in the catalyst was determined by ultraviolet visible light spectroscopy (DRUVS). The instrument adopts a Cary300 ultraviolet visible light analyzer of Agilent, and the wavelength range is as follows: 190 nm-1100 nm, wavelength precision: ± 0.1nm, wavelength reproducibility: ± 0.1nm, baseline stability: 0.0003/h, stray light: 0.02% or less, photometric accuracy: + -0.003.

In the following examples and comparative examples, the strength of the force between the active component and the carrier in the catalyst was characterized by laser raman spectroscopy. The instrument adopts LabRAM HR UV-NIR type confocal micro-Raman spectrometer of Jobin Yvon France, an excitation light source is 325nm monochromatic laser of a HeCd laser of Kimmon corporation, japan, a microscope system is a Japan Olympus microscope coupled on the spectrometer, an ultraviolet 15-time objective lens is adopted, a confocal pinhole adopts 100 mu m, and the peak position adopts a first-order peak of monocrystalline silicon (520.7 cm) ^-1 ) To correct it.

The activity of the catalyst is characterized by desulfurization rate, denitrification rate, carbon residue removal rate and demetalization rate, and the activity stability of the catalyst is characterized by the change of the desulfurization rate, the denitrification rate, the carbon residue removal rate and the demetalization rate after the catalyst works for 100 hours and 1000 hours.

Example 1

This example is intended to illustrate the preparation of the heavy oil hydrogenation catalyst of the present invention.

Mixing uniformly the dry powder RPB100 of pseudo-boehmite produced by 1 kg of Changling catalyst factory and 30 g of sesbania powder, mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder to form plastic bodies, extruding the plastic bodies into butterfly-shaped strips with the diameter of 1.1 mm, drying the wet strips at 120 ℃ for 3 hours, heating the wet strips to 630 ℃ at 200 ℃/hour, and keeping the temperature at 630 ℃ for 4 hours to obtain the nickel-containing carrier.

Weighing 100 g of the nickel-containing carrier, and using 120 ml of MoO-containing carrier ₃ 148 g/L of mixed solution of molybdenum oxide and phosphoric acid is soaked for 1 hour, dried for 3 hours at 110 ℃, and activated for 3 hours at 400 ℃ to prepare the catalyst.

The total weight of the heavy oil hydrogenation catalyst is taken as a reference, a carbon-sulfur analyzer is adopted to determine the sulfur content in the catalyst, and an ultraviolet visible light spectrum method is adopted to determine the nickel aluminate spinel NiAl on the catalyst carrier ₂ O ₄ The strength of acting force between the active component and the carrier in the catalyst is represented by a laser Raman spectroscopy, the content of the catalyst component is measured by an X-ray fluorescence spectrometer, and the measurement result is shown in Table 1.

Example 2

This example illustrates the preparation of the heavy oil hydrogenation catalyst of the present invention.

The preparation method comprises the steps of uniformly mixing 1 kg of pseudo-boehmite dry glue powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid, extruding the mixture into a butterfly-shaped strip with the diameter of 1.1 mm after kneading the mixture on a double-screw extruder into a plastic body, drying the wet strip at 120 ℃ for 3 hours, heating the wet strip to 650 ℃ at 200 ℃/hour, and keeping the temperature at 650 ℃ for 4 hours to obtain the nickel-containing carrier.

Weighing 100 g of the nickel-containing carrier, and adding 120 ml of MoO-containing carrier ₃ 148 g/L of mixed solution of ammonium molybdate and ammonia water is immersed for 1 hour, dried for 3 hours at 110 ℃, and activated for 3 hours at 400 ℃ to prepare the catalyst.

Taking the total weight of the heavy oil hydrogenation catalyst as a reference, measuring the sulfur content in the catalyst by adopting a carbon-sulfur analyzer, and measuring the nickel-aluminum spinel NiAl on the catalyst carrier by adopting an ultraviolet visible light spectrum method ₂ O ₄ The strength of acting force between the active component and the carrier in the catalyst is represented by a laser Raman spectroscopy, the content of the catalyst component is measured by an X-ray fluorescence spectrometer, and the measurement result is shown in Table 1.

Example 3

The preparation method comprises the steps of uniformly mixing 1 kg of pseudo-boehmite dry glue powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid, extruding the mixture into a butterfly-shaped strip with the diameter of 1.1 mm after kneading the mixture on a double-screw extruder, drying the wet strip at 120 ℃ for 3 hours, heating to 780 ℃ at 200 ℃/hour, and keeping the temperature at 780 ℃ for 4 hours to obtain the nickel-containing carrier.

Weighing 100 g of the nickel-containing carrier, and using 120 ml of MoO-containing carrier ₃ 148 g/l of mixed solution of ammonium molybdate and ammonia water is soaked for 1 hour, dried for 3 hours at 110 ℃, and then activated for 3 hours at 400 ℃ to prepare the catalyst.

Example 4

Mixing uniformly the dry powder RPB100 of pseudo-boehmite produced by 1 kg of Changling catalyst factory and 30 g of sesbania powder, mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of nitric acid, extruding the mixture into a butterfly-shaped strip with the diameter of 1.1 mm after kneading the mixture on a double-screw extruder, drying the wet strip at 120 ℃ for 3 hours, heating to 630 ℃ at 200 ℃/hour, and keeping the temperature at 630 ℃ for 4 hours to obtain the nickel-containing carrier.

Comparative example 1

The preparation method comprises the steps of uniformly mixing 1 kg of pseudo-boehmite dry glue powder RPB100 produced by a long-distance catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid at room temperature, extruding into butterfly-shaped strips with the diameter of 1.1 mm after kneading into plastic bodies on a double-screw extruder, drying wet strips at 120 ℃ for 3 hours, heating to 400 ℃ at 200 ℃/hour, and keeping the temperature at 400 ℃ for 4 hours to obtain the nickel-containing carrier.

Determining the sulfur content in the catalyst by a carbon-sulfur analyzer based on the total weight of the heavy oil hydrogenation catalystMeasuring nickel aluminate spinel NiAl on catalyst carrier by ultraviolet visible light spectrum method ₂ O ₄ The strength of acting force between the active component and the carrier in the catalyst is represented by a laser Raman spectroscopy, the content of the catalyst component is measured by an X-ray fluorescence spectrometer, and the measurement result is shown in Table 1.

Comparative example 2

The preparation method comprises the steps of uniformly mixing 1 kg of pseudo-boehmite dry glue powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid, extruding the mixture into a butterfly-shaped strip with the diameter of 1.1 mm after kneading the mixture on a double-screw extruder into a plastic body, drying the wet strip at 120 ℃ for 3 hours, heating the wet strip to 900 ℃ at 200 ℃/hour, and keeping the temperature at 900 ℃ for 4 hours to obtain the nickel-containing carrier.

Comparative example 3

The preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry rubber powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder by a conventional method, uniformly mixing the mixture with 1.2L of sulfuric acid aqueous solution containing 39 g/L of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder into a plastic body, extruding the plastic body into butterfly-shaped strips with phi of 1.1 mm, drying wet strips at 120 ℃ for 3 hours, heating to 800 ℃ at 200 ℃/hour, and keeping the temperature at 800 ℃ for 4 hours to obtain the carrier.

Weighing 100 g of the carrier, and using 120 ml of MoO-containing carrier ₃ 154 g/l NiO 37 gThe catalyst is prepared by soaking the mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid for 1 hour per liter, drying the mixed solution at 120 ℃ for 3 hours and activating the mixed solution at 400 ℃ for 3 hours.

Taking the total weight of the heavy oil hydrogenation catalyst as a reference, measuring the sulfur content in the catalyst by adopting a carbon-sulfur analyzer, and measuring the nickel-aluminum spinel NiAl on the catalyst by adopting an ultraviolet visible light spectrum method ₂ O ₄ The strength of acting force between the active component and the carrier in the catalyst is represented by a laser Raman spectroscopy, the content of the catalyst component is measured by an X-ray fluorescence spectrometer, and the measurement result is shown in Table 1.

Comparative example 4

The preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry glue powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.2 l of sulfuric acid aqueous solution containing 39 g/l of sulfuric acid at room temperature, kneading the mixture into a plastic body on a double-screw extruder, extruding the plastic body into butterfly-shaped strips with the diameter of 1.1 mm, drying wet strips at the temperature of 120 ℃ for 3 hours, and roasting the strips at the temperature of 800 ℃ for 3 hours to obtain a carrier.

Weighing 100 g of the carrier, and using 120 ml of MoO-containing carrier ₃ 154 g/L and 37 g/L NiO, soaking the mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid for 1 hour, drying the mixed solution at 120 ℃ for 2 hours, heating the dried catalyst to 650 ℃ at 300 ℃/hour, and keeping the temperature of 650 ℃ for 3 hours to obtain the catalyst.

Based on the total weight of the heavy oil hydrogenation catalyst, a carbon-sulfur analyzer is adopted to determine the sulfur content in the catalyst, and an ultraviolet visible light spectrum method is adopted to determine nickel aluminate spinel NiAl on the catalyst ₂ O ₄ The strength of acting force between the active component and the carrier in the catalyst is represented by a laser Raman spectroscopy, the content of the catalyst component is measured by an X-ray fluorescence spectrometer, and the measurement result is shown in Table 1.

TABLE 1

Test example

The catalysts of examples 1 to 4 and comparative examples 1 to 4 were used for hydrogenation reactions to evaluate their respective catalytic performances.

The catalyst was evaluated on a 100 ml small fixed bed reactor using an atmospheric residue having a nickel content of 19ppm, a vanadium content of 27ppm, a sulfur content of 3.1%, a carbon residue of 11%, and a nitrogen content of 0.3% as a raw material (these are in weight percent concentrations).

The catalysts obtained above are respectively crushed into particles with the diameter of 0.8-1.2 mm, and the loading of the catalyst is 100 ml. The reaction conditions are as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14 MPa, and the liquid hourly space velocity is 0.6 h ^-1 And the volume ratio of hydrogen to oil is 1000, samples are taken after the reaction is carried out for 100 hours and 1000 hours respectively, and the content of nickel and vanadium in the treated oil is measured by adopting an inductively coupled plasma emission spectrometer (ICP-AES). (the instrument is PE-5300 type plasma light meter of PE company, USA, the concrete method is shown in petrochemical analysis method RIPP 124-90)

The sulfur content was measured by an electric method (see petrochemical analysis method RIPP 62-90).

The nitrogen content is measured by an electric method (see petrochemical analysis method RIPP 63-90).

The carbon residue content is determined by a micro-method (the specific method is shown in petrochemical analysis method RIPP 148-90).

The removal rates of sulfur, carbon residue, nitrogen and metals were calculated according to the following formulas:

the results of removing impurities of the catalysts of examples 1 to 4 and comparative examples 1 to 4 are shown in Table 2.

TABLE 2

As can be seen from the results in Table 2, the overall impurity removal activity stability of the catalyst of the present invention is significantly improved compared with the prior art, the initial reaction activity of the catalyst (i.e., the removal performance of each impurity after 100 hours of operation) is close to the level of the prior art, but the reaction stability of the catalyst (i.e., the reduction of the removal performance of each impurity after 1000 hours of operation) is greatly improved, so that the overall performance of the catalyst is significantly improved. Therefore, the catalyst provided by the invention greatly prolongs the service life of the catalyst and improves the production efficiency on the premise of meeting the basic activity requirement, and has a good application prospect.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.

Claims

1. A heavy oil hydrogenation catalyst, comprising:

a support comprising an inorganic refractory oxide, nickel oxide and a composite thereof, the composite being a nickel aluminate spinel;

wherein the absorbances at 630nm and 500nm of the carrier are respectively F when the carrier is measured by diffuse reflection ultraviolet visible spectrum ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ 1.3 to 3.0; and

the active component comprises at least one VIB group metal, and the content of the active component is 8-30% calculated by oxides and based on the total weight of the heavy oil hydrogenation catalyst;

wherein, in the Raman spectrum of the heavy oil hydrogenation catalyst, the Raman spectrum is positioned at 940cm ^-1 Intensity of nearby characteristic peak and intensity of 840cm ^-1 The intensities of the near characteristic peaks are respectively I ₉₄₀ And I ₈₄₀ And the ratio of the two K = I ₉₄₀ /I ₈₄₀ Is 1.0 to 2.4.

2. The heavy oil hydrogenation catalyst of claim 1, wherein the inorganic refractory oxide is alumina.

3. The heavy oil hydrogenation catalyst of claim 1, wherein the nickel content is from 1% to 8% as an oxide and based on the total weight of the heavy oil hydrogenation catalyst.

4. The heavy oil hydrogenation catalyst of claim 1, wherein the active component further comprises one or more of a group VIII metal.

5. The heavy oil hydrogenation catalyst of claim 4, wherein when the group VIII metal is nickel, the group VIII metal is present in an amount of 0.1 to 3% by weight on an oxide basis and based on the total weight of the heavy oil hydrogenation catalyst, and the total nickel content of the heavy oil hydrogenation catalyst is not more than 8%.

6. The heavy oil hydrogenation catalyst of claim 1, wherein the support further comprises a promoter selected from the group consisting of a metallic promoter and/or a non-metallic promoter.

7. The heavy oil hydrogenation catalyst of claim 6, wherein the promoter is a metal promoter, and the content of the metal promoter is 0.1% to 3% by element and based on the total weight of the heavy oil hydrogenation catalyst.

8. The heavy oil hydrogenation catalyst of claim 6, wherein the promoter is a non-metallic promoter, and the content of the non-metallic promoter is 0.5 to 15% by element and based on the total weight of the heavy oil hydrogenation catalyst.

9. The heavy oil hydrogenation catalyst of claim 1, wherein the at least one group VIB metal is molybdenum and/or tungsten.

10. A method for preparing a heavy oil hydrogenation catalyst as claimed in claim 1, comprising the steps of:

mixing an inorganic heat-resistant oxide precursor, a nickel source and a forming auxiliary agent to obtain a mixture, and forming;

roasting the formed product at 600-800 ℃ for 1-10 h to obtain a carrier; and

and (2) dipping the carrier in a solution containing an active component, drying the dipped product, and activating at the temperature of 300-550 ℃ to obtain the heavy oil hydrogenation catalyst.

11. The method of claim 10, wherein the firing temperature is 650 ℃ to 730 ℃.

12. The method according to claim 10, wherein the temperature increase rate of the calcination is 50 ℃/hr to 600 ℃/hr.

13. The preparation method according to claim 10, wherein the inorganic refractory oxide precursor is pseudo-boehmite, and the nickel source is one or more selected from nickel nitrate, nickel sulfate and basic nickel carbonate; the solution containing the active component is an aqueous solution containing at least one group VIB metal oxide or salt selected from one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, tungsten oxide, ammonium tungstate and ammonium paratungstate.

14. The method of claim 10, further comprising adding a promoter precursor to the mixture before the forming process, such that the catalyst support contains a promoter selected from the group consisting of metal promoters and non-metal promoters.

15. The method according to claim 10, wherein the forming aid comprises a peptizing agent selected from one or more of an aqueous nitric acid solution, an aqueous hydrochloric acid solution and an aqueous citric acid solution, and a lubricant selected from one or more of sesbania powder, citric acid, starch and carboxymethyl cellulose.

16. The production method according to claim 10, wherein the molding process includes:

kneading the mixture to obtain a plastic body;

drying the plastic body after molding to obtain a molded product;

wherein the shaping method is selected from one or more of extruding, rolling ball, tabletting and granulating.

17. The method according to claim 16, wherein the drying temperature is 100 ℃ to 250 ℃ and the drying time is 1h to 6h.

18. Use of the heavy oil hydrogenation catalyst according to any one of claims 1 to 9 in a heavy oil hydrogenation reaction.