CN115990487B - Hydrogenation catalyst and heavy oil hydrotreating method - Google Patents

Abstract

The present invention discloses a hydrogenation catalyst, comprising a sulfur-containing alumina carrier and a hydrogenation active metal component loaded on the carrier, wherein the active metal component is at least one metal component of the VIB group and at least one metal component of the VIII group, wherein the sulfur content in the sulfur-containing alumina carrier is 0.2-4.0wt% in terms of sulfur element. The sulfur-containing alumina carrier is prepared according to the following steps: (1) mixing hydrated alumina with an organic compound having a proton acceptor site to obtain a molded product; (2) subjecting the molded product obtained in step (1) to a first calcination and a second calcination in an oxygen-containing atmosphere; the hydrated alumina contains sulfur element, the temperature of the first calcination in step (2) does not exceed 500° C., and the carbon content in the molded product in terms of element in the first calcination is not higher than 1.0wt%. The catalyst of the present invention adopts an environmentally friendly sulfur-containing alumina carrier, and when applied to a heavy oil hydrogenation reaction, it exhibits good de-doping activity and activity stability.

Description

A hydrogenation catalyst and a heavy oil hydrogenation treatment method

Technical Field

The present invention relates to the field of hydrogenation catalysts, and in particular to a hydrogenation catalyst containing an environmentally friendly sulfur-containing alumina carrier and application of the catalyst in heavy oil hydrogenation treatment.

Background technique

Heavy oil hydroprocessing catalyst is the core of achieving heavy oil lightening. With the heavy and inferior quality of crude oil and increasingly stringent environmental regulations, how to efficiently and greenly produce heavy oil hydroprocessing catalyst has become a key issue restricting the benefits of catalyst manufacturers, among which the environmental protection issue in the preparation process of alumina carrier is particularly prominent. In the preparation process of a certain type of sulfur-containing alumina carrier, due to the presence of sulfur, it is very easy to decompose and generate SO ₂ during the roasting process, and SO ₂ is one of the most important air pollutants, causing great damage to the environment. Therefore, how to solve the SO ₂ emission problem is a prominent problem faced by catalyst manufacturers.

In response to this problem, many solutions focus on the development of flue gas desulfurization technology after roasting, such as the most widely used limestone-gypsum wet desulfurization technology. However, this technology eventually makes limestone a new solid waste, causing secondary pollution. At the same time, the desulfurization byproduct _CO2 increases carbon emissions, and the consumed limestone resources are also a non-renewable mineral resource. In recent years, emerging desulfurization technologies include catalytic oxidation desulfurization technology, biological desulfurization technology, and ozone oxidation technology. Catalytic technology can not only achieve effective utilization of resources, but also has low energy consumption and is green and pollution-free. It is a major trend in the development of flue gas desulfurization and denitrification technology. However, there are still major deficiencies in catalyst activity, anti-toxicity and service life. Based on this, the development of environmentally friendly heavy oil hydrogenation catalysts with excellent performance has become a common pursuit of technicians in this field.

Summary of the invention

In view of the problems existing in the prior art, the present invention provides a hydrogenation catalyst containing a sulfur-containing alumina carrier and its application. The preparation process of the catalyst is environmentally friendly and is applied to heavy oil hydrogenation reaction. It has good hydrogenation and decontamination activity and activity stability. Specifically, the main contents of the present invention are as follows:

The present invention provides a hydrogenation catalyst, comprising a sulfur-containing alumina carrier and a hydrogenation active metal component supported on the carrier, wherein the active metal component is at least one metal component of Group VIB and at least one metal component of Group VIII, and based on the catalyst, the content of the metal component of Group VIB calculated as oxide is 5-35% by weight, and the content of the metal component of Group VIII is 0.5-15% by weight; wherein the sulfur content of the sulfur-containing alumina carrier calculated as sulfur element is 0.2-4.0wt%.

The present invention provides an important hydrogenation treatment method, comprising contacting heavy crude oil with the catalyst provided by the present invention under heavy oil hydrogenation reaction conditions.

The catalyst of the present invention adopts an environmentally friendly sulfur-containing alumina carrier, which can significantly reduce or eliminate the generation of sulfur dioxide during the catalyst preparation process, reduce environmental pollution, reduce the equipment investment for back-end pollution control, and realize the environmentally friendly production of high-performance carriers. The obtained catalyst has good hydrogenation and decontamination performance and good activity stability.

Detailed ways

In order to enable those skilled in the art to better understand the present invention and its advantages, and thus implement the present invention, the technical solution of the present invention will be explained below with reference to specific implementation methods.

According to the hydrogenation catalyst provided by the present invention, it comprises a sulfur-containing alumina carrier and a hydrogenation active metal component loaded on the carrier, wherein the active metal component is at least one metal component of Group VIB and at least one metal component of Group VIII, and based on the catalyst, the content of the metal component of Group VIB calculated as oxide is 5-35% by weight, and the content of the metal component of Group VIII is 0.5-15% by weight; wherein the sulfur content of the sulfur-containing alumina carrier calculated as sulfur element is 0.2-4.0wt%.

According to the present invention, in order to obtain a catalyst with better performance and a more environmentally friendly preparation process, the sulfur-containing alumina carrier of the present invention is preferably prepared by the following steps: (1) mixing hydrated alumina with an organic compound having a proton acceptor site and extruding a strip to obtain a molded product; (2) subjecting the molded product obtained in step (1) to a first calcination and a second calcination in an oxygen-containing atmosphere; wherein the hydrated alumina contains sulfur element, the temperature of the first calcination in step (2) does not exceed 500°C, and the first calcination causes the carbon content in the molded product to be no higher than 1.0wt% in terms of element.

In the preparation process of sulfur-containing alumina carrier, various additives such as extrusion aids and peptizers are usually added for better extrusion molding. The sulfur element in hydrated alumina can exist in various forms. In some cases, the substances containing sulfur in hydrated alumina can exist relatively stably and have good high temperature resistance. However, when it coexists with additives such as extrusion aids and peptizers, the sulfur-containing species are easily converted into sulfur dioxide during high-temperature roasting. On the one hand, it will make the final alumina carrier contain no sulfur or the sulfur content is too low. More importantly, the released sulfur dioxide has an extremely adverse effect on the environment.

After in-depth research, the inventors of the present invention found that when the alumina carrier precursor is treated by a staged calcination method, controlling the temperature of the first stage calcination and the carbon content of the first stage calcination product can inhibit the generation of sulfur dioxide, obtain a high-performance sulfur-containing alumina carrier, and reduce or eliminate the generation of sulfur dioxide.

According to the present invention, the sulfur element in the hydrated alumina is not particularly limited in form, and can be present in one or more forms of sulfate, sulfite, thiosulfate, sulfide, and sulfur, preferably in the form of sulfate and/or sulfite. The sulfur content in the hydrated alumina is not particularly limited, and generally depends on the requirements for the sulfur content in the alumina carrier. Generally, the sulfur content is 0.2-4.0wt% based on the dry basis of the hydrated alumina and calculated as sulfur element, preferably 0.3-3.5wt%.

According to the present invention, the components in step (1) are used in conventional amounts and proportions. For example, relative to 100 parts by weight of the hydrated alumina, the content of the organic compound having proton acceptor sites is 1-25 parts by weight, preferably 2-20 parts by weight, more preferably 3-15 parts by weight, and further preferably 3.5-10 parts by weight.

In the organic compound having a proton acceptor site of the present invention, the proton acceptor site refers to an element that can form a hydrogen bond with water, such as one or more of F, O and N;

Preferably, the organic compound having a proton acceptor site is a compound containing a hydroxyl group in its molecular structure;

More preferably, the organic compound having a proton acceptor site is a polyhydroxy organic compound;

Further preferably, the organic compound having a proton acceptor site is a polysaccharide and/or an etherified product of a polysaccharide;

More preferably, the organic compound having a proton acceptor site is one or more of galactan, mannan, galactomannan and cellulose ether, and the cellulose ether is preferably one or more of methyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose;

Particularly preferably, the compound having at least two proton acceptor sites is galactomannan and cellulose ether. Preferably, based on the total amount of the compound having at least two proton acceptor sites, the content of galactomannan is 10-70% by weight, preferably 15-68% by weight, more preferably 20-65% by weight; the content of cellulose ether is 30-90% by weight, preferably 32-85% by weight, more preferably 35-80% by weight.

The hydrated alumina described in the present invention can be prepared by conventional means in the art, wherein the sulfur element contained therein can be introduced during the preparation, or can be added after the hydrated alumina is formed, as long as the sulfur element content meets the requirements. The hydrated alumina can be one or more selected from alumina trihydrate and alumina monohydrate. The hydrated alumina preferably contains alumina monohydrate, more preferably alumina monohydrate. Specific examples of the hydrated alumina may include but are not limited to boehmite, alumina trihydrate, amorphous hydrated alumina and pseudo-boehmite. In a preferred embodiment of the present invention, the hydrated alumina contains pseudo-boehmite, more preferably pseudo-boehmite.

Alumina hydrate can be mixed with an organic compound having a proton acceptor site by conventional methods. Alumina hydrate can be mixed with an organic compound having a proton acceptor site under shearing. In one embodiment, the mixing method is stirring. Alumina hydrate and an organic compound having a proton acceptor site can be placed in a container with a stirring device, and the two can be mixed evenly by stirring to obtain the hydrated alumina composition. The stirring can be carried out in a container with a stirring device or in a beater. In another embodiment, the mixing method is kneading. Alumina hydrate and an organic compound having a proton acceptor site can be kneaded in a kneader to obtain the hydrated alumina composition. The type of the kneader is not particularly limited. Stirring and kneading can be used in combination to mix alumina hydrate with an organic compound having a proton acceptor site. At this time, it is preferred to stir first and then knead.

During the mixing process, water may be added or not. Generally, water may be added during the mixing process from the perspective of improving the uniformity of the mixing. Generally, the weight ratio of the added water to the organic compound having a proton acceptor site may be 5-15:1. Preferably, it is 8-12:1. During the mixing process, a peptizing agent may also be added, but preferably, no peptizing agent is added.

In step (1), the molding method is not particularly limited, and various molding methods commonly used in the art can be used, such as extrusion, spraying, spheronization, tableting, or a combination thereof. In a preferred embodiment of the present invention, molding is performed by extrusion.

In step (1), the formed object can have various shapes according to specific use requirements, for example, one or more of spherical, honeycomb, bird's nest, sheet or strip (such as clover, disc, cylinder and Raschig ring).

According to the present invention, the purpose of the first roasting is to remove all or most of the organic matter in the molded product so that the carbon content in the product obtained after the first roasting is maintained at a low level. At the same time, the first roasting temperature must be controlled to avoid the conversion of sulfur element into sulfur dioxide during the first roasting process.

Under preferred conditions, according to the method provided by the present invention, the first calcination makes the carbon content in the carrier in terms of element not higher than 0.8wt%, preferably not higher than 0.6wt%. In order to better control, the conditions of the first calcination are preferably: the calcination temperature is 300-550°C, more preferably 350-500°C, more preferably 400-480°C; the calcination time is 1-20 hours, more preferably 1.5-15 hours, more preferably 2-10 hours, and more preferably 2-6 hours; the oxygen-containing atmosphere may include nitrogen and/or inert gas in addition to oxygen, and there is no special requirement for the volume content of oxygen in the oxygen-containing atmosphere, for example, it may be 10-100%, preferably 20-50%.

The purpose of the second calcination is to make the alumina molded product undergo a phase change, transform it into γ-phase alumina, and obtain an alumina carrier with a stable structure. The conditions of the second calcination are conventional conditions in the art, the second stage calcination temperature can be 560-1200°C, preferably 600-1000°C, more preferably 650-850°C, and the calcination time can be 1-20 hours, preferably 1.5-15 hours, more preferably 2-10 hours, and further preferably 2-6 hours.

When performing each stage of roasting, the temperature can be raised to the roasting temperature at a conventional rate. Generally, the temperature in the container containing the molded product can be raised to the roasting temperature at a rate of 10-400°C/hour, preferably 30-350°C/hour, more preferably 60-300°C/hour, and further preferably 100-250°C/hour. The temperature in the container containing the molded product can be raised from the ambient temperature to the first stage roasting temperature. If a drying step is included, the temperature in the container containing the molded product can also be raised from the drying temperature to the first stage roasting temperature. There is no particular limitation.

In addition, when the water content in the hydrated alumina is relatively high, a drying step may be included before the staged roasting, that is, between step (1) and step (2). The drying conditions include: a temperature of 60-280°C, preferably 80-250°C, more preferably 110-200°C, and a drying time of 1-48 hours, preferably 2-24 hours, more preferably 2-12 hours.

The present invention also includes a method for obtaining a hydrogenation catalyst by loading a hydrogenation active metal component on a sulfur-containing alumina carrier prepared by any of the above methods. The loading method is preferably an impregnation method, comprising impregnating the sulfur-containing alumina carrier in a solution of a compound containing an active metal component, and then drying and calcining to obtain the hydrogenation catalyst. Among them, the specific impregnation method and the type and content of the hydrogenation active metal component in the hydrogenation catalyst finally obtained are conventionally selected in the art. In order to make the hydrogenation catalyst show better heteroatom removal activity in the hydrogenation reaction, preferably, the VIB group metal is molybdenum and/or tungsten, and the VIII group metal is nickel and/or cobalt: the amount of each component is such that the content of the VIB group metal component based on the total weight of the hydrogenation catalyst and calculated as oxide is 5-35% by weight, and the content of the VIII group metal component is 0.5-15% by weight. Further preferably, based on the total weight of the hydrogenation catalyst, the content of CoO is 0.5-15% by weight, further preferably 2-8% by weight, more preferably 3-7% by weight, and most preferably 3-5% by weight: the content of MoO3 is 5-35% by weight, further preferably 8-30% by weight, more preferably 10-25% by weight, and most preferably 12-25% by weight: the content of NiO is 0.5-15% by weight, further preferably 2-8% by weight, more preferably 3-7% by weight, and most preferably 3-5% by weight; the content of WO3 is 5-35% by weight, further preferably 5-30% by weight, more preferably 10-30% by weight, and most preferably 15-25% by weight.

The present invention does not particularly limit the impregnation conditions in the preparation process of the hydrogenation catalyst, as long as the active metal components can be loaded on the environmentally friendly alumina carrier. For example, the impregnation conditions include an impregnation temperature of 20-300°C, preferably 50-100°C; an impregnation time of 1-20 hours, preferably 1-6 hours.

After the sulfur-containing alumina carrier is impregnated with the solution containing the hydrogenation active metal component, it is usually necessary to dry and calcine. The drying process in the preparation process of the hydrogenation catalyst of the present invention can be oven drying or vacuum drying. The drying conditions can be conventionally selected in the art, for example, the drying conditions include a drying temperature of 80-200°C, preferably 80-180°C, more preferably 80-150°C; the drying time can be 1-10 hours, preferably 2-8 hours, more preferably 2-6 hours.

The present invention does not particularly limit the calcination conditions. For example, the calcination conditions generally include: the calcination temperature can be 300-900°C, preferably 300-800°C, and more preferably 400-800°C; the calcination time can be 1-10 hours, preferably 2-8 hours, and more preferably 2-6 hours.

The present invention also provides the use of the above hydrogenation catalyst in heavy oil hydrogenation reaction, comprising contacting heavy feedstock oil with the hydrogenation catalyst or the hydrogenation catalyst obtained by the method under heavy oil hydrogenation reaction conditions. In the heavy oil hydrodesulfurization method, the main improvement of the present invention is the use of a new hydrogenation catalyst, and the heavy feedstock oil and heavy oil hydrogenation reaction conditions used can be the same as those in the prior art, which will not be described in detail here.

The following examples will further illustrate the present invention, but should not be construed as limiting the present invention. In these examples, the reagents used, unless otherwise specified, are chemically pure reagents and can be purchased from the market.

In the following examples and comparative examples, the carbon content of alumina after the first calcination is determined by an infrared carbon and sulfur element analyzer. The analysis method is as follows: using HORIBA's EMIA-920V carbon and sulfur analyzer, the sample and the flux are placed in a high-frequency induction furnace, and then oxygen is introduced. The sample is burned at high temperature to generate gases such as CO, _CO2 and _SO2 . After dehydration and impurities, the gas enters the infrared absorption cell. According to the changes in the infrared light absorption intensity of different gases, the instrument automatically calculates the carbon content of the sample (for specific methods, see petrochemical analysis method HG/T 5594); the sulfur content in the alumina dry strip after extrusion molding and the sulfur-containing alumina carrier after the second calcination is determined by an X-ray fluorescence spectrometer (i.e., XRF). The analysis method is as follows: using a 3271 X-ray fluorescence spectrometer from Rigaku Corporation, a scintillation counter and a proportional counter are used to detect the element spectral line intensity, and the element content is quantitatively and semi-quantitatively analyzed by an external standard method. Experimental conditions: powder sample tableting, rhodium target, laser voltage 50 kV, laser current 50 mA (for specific methods, see petrochemical analysis method RIPP 133-90). The sulfur content in the alumina dry strip is based on the alumina dry basis (alumina dry strip is calcined at 400°C for 3 hours).

The activity of the catalyst is characterized by the desulfurization rate, denitrification rate, residual carbon removal rate and demetallization rate. The activity stability of the catalyst is characterized by the changes in the desulfurization rate, denitrification rate, residual carbon removal rate and demetallization rate after the catalyst has worked for 100 hours and 1000 hours.

Example 1

Preparation of sulfur-containing alumina carrier

1 kg of pseudo-boehmite dry rubber powder, 50 g of galactomannan, and 50 g of methylcellulose were mixed evenly, and then 1200 ml of aqueous solution was added. After being kneaded into a plastic body on a twin-screw extruder, it was extruded into butterfly-shaped strips of Φ1.3 mm. After the wet strips were dried at 120°C for 3 hours, alumina dry strips Z1 were obtained; then the alumina dry strips were calcined in stages, and the first stage was heated to 450°C at 200°C/hour and kept at 450°C for 3 hours, and the alumina obtained was F1; the second stage was heated to 750°C at 200°C/hour and kept at 750°C for 3 hours to obtain sulfur-containing alumina carrier A1. The sulfur content on the carrier was determined by X-ray fluorescence spectrometry, and the results are shown in Table 1.

Preparation of hydrogenation catalyst

Molybdenum oxide and basic cobalt carbonate were dispersed in water to form an impregnation solution, wherein the concentration of _MoO3 was 197.4 g/L and the concentration of basic cobalt carbonate was 47.6 g/L in terms of CoO. The impregnation solution was used to saturate the A1 carrier at ambient temperature (25°C) for 1 hour. The impregnated alumina strips were dried at 120°C and normal pressure in an air atmosphere for 2 hours, and then calcined at 400°C and normal pressure in an air atmosphere for 3 hours to obtain catalyst C1. The CoO content in the catalyst was 3.5 wt%, and ^the _MoO3- content was 14.5 wt%.

Example 2

Preparation of sulfur-containing alumina carrier

1 kg of pseudo-boehmite dry rubber powder, 50 g of galactomannan, and 50 g of methylcellulose were mixed evenly, and then 1200 ml of aqueous solution was added. After being kneaded into a plastic body on a twin-screw extruder, it was extruded into butterfly-shaped strips of Φ1.3 mm. After the wet strips were dried at 120°C for 3 hours, alumina dry strips Z2 were obtained; then the alumina dry strips were calcined in stages, and the first stage was heated to 400°C at 200°C/hour and kept at 400°C for 3 hours, and the alumina obtained was F2; the second stage was heated to 750°C at 200°C/hour and kept at 750°C for 3 hours to obtain sulfur-containing alumina carrier A2. The sulfur content on the catalyst was determined by X-ray fluorescence spectrometry, and the results are shown in Table 1.

Preparation of hydrogenation catalyst

The catalyst was prepared by the same method as in Example 1, except that the carrier was A2, and the composition of the prepared catalyst C2 was the same as C1.

Example 3

Preparation of sulfur-containing alumina carrier

1 kg of pseudo-boehmite dry rubber powder, 50 g of galactomannan and 50 g of methyl cellulose were mixed evenly, and then 1200 ml of aqueous solution was added. After kneading into a plastic body on a twin-screw extruder, it was extruded into butterfly-shaped strips of Φ1.3 mm. After the wet strips were dried at 120°C for 3 hours, dry alumina strips Z3 were obtained; then the dry alumina strips were calcined in stages. In the first stage, the temperature was increased to 450°C at 200°C/hour and kept at 450°C for 5 hours. The obtained alumina was F3; in the second stage, the temperature was increased to 750°C at 200°C/hour and kept at 750°C for 3 hours to obtain sulfur-containing alumina carrier A3.

Preparation of hydrogenation catalyst

The catalyst was prepared by the same method as in Example 1, except that the carrier was A3, and the composition of the prepared catalyst C3 was the same as C1.

Comparative Example 1

1 kg of pseudo-boehmite dry rubber powder, 50 g of galactomannan and 50 g of methyl cellulose were mixed evenly, and then 1200 ml of aqueous solution was added. After kneading into a plastic body on a twin-screw extruder, it was extruded into butterfly-shaped strips of Φ1.3 mm. After the wet strips were dried at 120°C for 3 hours, alumina dry strips DZ1 were obtained; then the alumina dry strips were calcined, the temperature was increased to 750°C at 200°C/hour, and the alumina carrier DA1 was obtained at a constant temperature of 750°C for 3 hours.

The catalyst was prepared by the same method as in Example 1, except that the carrier was DA1 and the composition of the prepared catalyst DC1 was the same as C1.

Comparative Example 2

1 kg of pseudo-boehmite dry rubber powder, 50 g of galactomannan and 50 g of methyl cellulose were mixed evenly, and then 1200 ml of aqueous solution was added. After kneading into a plastic body on a twin-screw extruder, it was extruded into butterfly-shaped strips of Φ1.3 mm. After the wet strips were dried at 120°C for 3 hours, dry alumina strips DZ2 were obtained; then the dry alumina strips were calcined in stages. In the first stage, the temperature was increased to 250°C at 200°C/hour and kept at a constant temperature of 250°C for 3 hours. The alumina obtained was DF2; in the second stage, the temperature was increased to 750°C at 200°C/hour and kept at a constant temperature of 750°C for 3 hours to obtain the alumina carrier DA2.

The catalyst was prepared by the same method as in Example 1, except that the carrier was DA2 and the composition of the prepared catalyst DC2 was the same as C1.

Comparative Example 3

1 kg of pseudo-boehmite dry rubber powder, 50 g of galactomannan and 50 g of methyl cellulose were mixed evenly, and then 1200 ml of aqueous solution was added. After kneading into a plastic body on a twin-screw extruder, it was extruded into butterfly-shaped strips of Φ1.3 mm. After the wet strips were dried at 120°C for 3 hours, dry alumina strips DZ3 were obtained; then the dry alumina strips were calcined in stages. In the first stage, the temperature was raised to 600°C at 200°C/hour and kept at 600°C for 3 hours. The alumina obtained was DF3; in the second stage, the temperature was raised to 750°C at 200°C/hour and kept at 750°C for 3 hours to obtain the alumina carrier DA3.

The catalyst was prepared by the same method as in Example 1, except that the carrier was DA3 and the composition of the prepared catalyst DC3 was the same as C1.

Example 4

Preparation of sulfur-containing alumina carrier

Compared with Example 1, the only difference is that the raw materials in step (1) are 1 kg of pseudo-boehmite dry rubber powder, 60 g of galactan and 80 g of hydroxypropyl cellulose. The obtained alumina dry strips, intermediate samples and molded bodies are respectively recorded as Z4, F4 and A4.

Preparation of hydrogenation catalyst

The catalyst was prepared by the same method as in Example 1, except that the carrier was A4, and the composition of the prepared catalyst C4 was the same as C1.

Example 5

Preparation of sulfur-containing alumina carrier

Compared with Example 1, the only difference is that the first stage calcination condition is to increase the temperature from 250°C/hour to 450°C and keep it at 450°C for 3 hours, and the second stage calcination condition is to increase the temperature from 200°C/hour to 800°C and keep it at 800°C for 3 hours. The obtained alumina dry strip, intermediate sample and molded body are respectively recorded as Z5, F5 and A5.

Preparation of hydrogenation catalyst

The catalyst was prepared by the same method as in Example 1, except that the carrier was A5, and the composition of the prepared catalyst C5 was the same as C1.

The carbon content of samples F1-F5 and DF2-DF3 was analyzed by infrared carbon-sulfur analyzer. The sulfur content of alumina dry strips Z1-Z5 and DZ1-DZ3, alumina carriers A1-A5 and DA1-DA3 prepared in each embodiment and comparative example was analyzed by XRF. The sulfur content loss rate during the preparation of the alumina carrier was calculated according to the following formula. The measurement results are shown in Table 1.

Table 1 Sulfur content loss rate during the preparation of alumina carrier

From the results in Table 1, it can be seen that compared with the comparative example, the samples in Examples 1 to 3 are calcined in two stages, and the carbon content after the first stage of calcination is controlled to be lower than 1.0wt%, and the sulfur content loss rate can be significantly reduced to obtain a sulfur-containing alumina carrier, and sulfur dioxide pollution can be reduced or even eliminated, with significant effects. The method of the present invention can significantly reduce the emission of _SO2 in the preparation process of the alumina carrier, and realize the efficient and green production of the sulfur-containing alumina carrier.

Examples 6-10 and Comparative Examples 4-6 respectively evaluated the catalytic performance of catalysts C1-C5 and comparative agents DC1-DC3.

The catalyst was evaluated in a 100 ml small fixed bed reactor using atmospheric residue oil with a nickel content of 19 ppm, a vanadium content of 27 ppm, a sulfur content of 3.1%, a residual carbon content of 11% and a nitrogen content of 0.3% as raw material (all the above concentrations are weight percentages).

The catalyst and contrast agent were crushed into particles with a diameter of 0.8 to 1.2 mm, and the catalyst loading was 100 ml. The reaction conditions were: reaction temperature 380°C, hydrogen partial pressure 14 MPa, liquid hourly space velocity 0.6 h ^-1 , hydrogen oil volume ratio 1000, and samples were taken after 100 hours and 1000 hours of reaction, and the nickel and vanadium contents in the treated oil were determined by inductively coupled plasma emission spectrometer (ICP-AES). (The instrument used was the PE-5300 plasma photometer of PE Company of the United States. For specific methods, see petrochemical analysis method RIPP124-90)

The sulfur content is determined by the coulometric method (for specific methods, see petrochemical analysis method RIPP62-90).

The nitrogen content was determined using the coulometric method (for specific methods, see petrochemical analysis method RIPP63-90).

The residual carbon content was determined by micro-method (for specific methods, see petrochemical analysis method RIPP148-90).

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

The results of catalyst impurity removal are shown in Table 2.

table 3

From the results in Table 2, it can be seen that the initial reaction activity of the catalyst (i.e., the removal performance of various impurities after 100 hours of operation) is slightly improved compared with the prior art, and the stability of the catalyst reaction (i.e., the decline in the removal performance of various impurities after 1000 hours of operation) is also improved to a certain extent. The catalyst production process of the present invention is more environmentally friendly, has better performance than the catalyst of the prior art, and has a significant effect.

Unless otherwise specified, the terms used in the present invention have the meanings commonly understood by those skilled in the art. The embodiments described in the present invention are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art may make various other substitutions, changes and improvements within the scope of the present invention. Therefore, the present invention is not limited to the above-mentioned embodiments, but is only defined by the claims.

Claims (24)

1. A hydrogenation catalyst comprising a sulfur-containing alumina carrier and a hydrogenation active metal component supported on the carrier, wherein the active metal component comprises at least one VIB group metal component and at least one VIII group metal component, the content of the VIB group metal component calculated by oxide is 5-35 wt% based on the catalyst, and the content of the VIII group metal component is 0.5-15 wt%; wherein the sulfur content of the sulfur-containing alumina carrier calculated by sulfur element is 0.2-4.0wt%;

wherein, the sulfur-containing alumina carrier is prepared according to the following steps:

(1) Mixing and extruding hydrated alumina with an organic compound with a proton acceptor site to obtain a molded product;

(2) Performing first roasting and second roasting on the molded product obtained in the step (1) in an oxygen-containing atmosphere;

the hydrated alumina contains sulfur, the temperature of the first roasting in the step (2) is not more than 500 ℃, and the first roasting ensures that the carbon content in terms of elements in a formed product is not more than 1.0wt%;

in the organic compound with proton acceptor site, the proton acceptor site is one or more than two of F, O and N which can form hydrogen bond with water;

The conditions for the first firing in step (2) include: the roasting temperature is 300-550 ℃, the roasting time is 1-20 hours, and the oxygen volume content in the oxygen-containing atmosphere is 10-100%;

the second stage roasting temperature is 560-1200 deg.c and roasting time is 1-20 hr.

2. The catalyst according to claim 1, wherein the sulfur element in the hydrated alumina is present in the form of one or more of sulfate, sulfite, sulfide, elemental sulfur, and the sulfur content is 0.2 to 4.0wt% on a dry basis of the hydrated alumina and calculated as elemental sulfur.

3. The catalyst of claim 2, wherein the sulfur content on a dry basis of hydrated alumina is 0.3 to 3.5wt% on elemental sulfur basis.

4. The catalyst of claim 2, wherein the amounts of the components in step (1) are such that: the content of the organic compound having a proton acceptor site is 1 to 25 parts by weight relative to 100 parts by weight of the hydrated alumina.

5. The catalyst according to claim 4, wherein the content of the organic compound having a proton acceptor site is 2 to 20 parts by weight.

6. The catalyst according to claim 5, wherein the content of the organic compound having a proton acceptor site is 3 to 15 parts by weight.

7. The catalyst according to claim 1, wherein the organic compound having a proton acceptor site is a compound having a hydroxyl group in a molecular structure.

8. The catalyst of claim 7, wherein the organic compound having a proton acceptor site is a polyhydroxy organic compound.

9. The catalyst of claim 8, wherein the organic compound having a proton acceptor site is a polysaccharide and/or an etherate of a polysaccharide.

10. The catalyst of claim 9, wherein the organic compound having a proton acceptor site is one or more of galactan, mannan, galactomannan, and cellulose ether, and the cellulose ether is one or more of methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

11. The catalyst of claim 10, wherein the organic compound having proton acceptor sites is a galactomannan and a cellulose ether, the galactomannan being present in an amount of 10 to 70 wt% based on the total amount of compounds having at least two proton acceptor sites: the cellulose ether is present in an amount of 30 to 90% by weight.

12. The catalyst of claim 11, wherein the galactomannan is present in an amount of 15-68 wt% based on the total amount of compounds having at least two proton acceptor sites: the cellulose ether is present in an amount of 32 to 85% by weight.

13. The catalyst of claim 1, wherein the hydrated alumina comprises pseudo-boehmite.

14. The catalyst of claim 13, wherein the alumina hydrate is pseudo-boehmite.

15. The catalyst according to claim 1, wherein the method of mixing in step (1) is stirring and/or kneading.

16. The catalyst of claim 1, wherein the first calcination results in a carbon content in elemental form in the support of no more than 0.8wt%.

17. The catalyst of claim 16, wherein the first calcination results in a carbon content in elemental form in the support of no more than 0.6wt%.

18. The catalyst of claim 1, wherein the conditions of the first calcination of step (2) comprise: the roasting temperature is 350-500 ℃, the roasting time is 1.5-15 hours, and the oxygen volume content in the oxygen-containing atmosphere is 20-50%.

19. The catalyst of claim 18, wherein the conditions of the first calcination of step (2) comprise: the roasting temperature is 400-480 ℃ and the roasting time is 2-10 hours.

20. The catalyst of claim 1, wherein the second stage calcination temperature is 600-1000 ℃ and the calcination time is 1.5-15 hours.

21. The catalyst of claim 20, wherein the second stage calcination temperature is 650-850 ℃ and the calcination time is 2-10 hours.

22. The catalyst of claim 1, wherein between step (1) and step (2) further comprises a step of drying, the drying conditions comprising: the temperature is 60-280 ℃, and the drying time is 1-48 hours.

23. The catalyst of claim 22, wherein the drying conditions comprise: the temperature is 80-250 ℃, and the drying time is 2-24 hours.

24. Use of the hydrogenation catalyst of any one of claims 1-23 in heavy oil hydrogenation reactions.