CN104927912B - Hydrotreatment method of hydrocarbon oil raw material with high content of metals - Google Patents

Abstract

A method for hydrotreating a hydrocarbon oil feedstock with high metal content, comprising: under hydrotreating reaction conditions, sequentially treating heavy feedstock oil with a hydrotreating protection catalyst I, a hydrotreating catalyst II and a hydrotreating catalyst III Catalyst combination contact, wherein, the hydroprocessing protected catalyst I contains a carrier and a hydrogenation active metal component supported on the carrier, the carrier contains alumina and at least one additive selected from boron, silicon and fluorine, Characterized by mercury porosimetry, the pore volume of the carrier is 0.5-1 ml/g, the specific surface area is 30-150 ^m2 /g, the most probable pore diameter is 80-300nm, and the carrier has a diameter of 12-15nm and A bimodal pore distribution with a diameter of 100-200nm, the pore volume of pores with a diameter of 12-15nm accounts for 10-22% of the total pore volume, and the pore volume of pores with a diameter of 100-200nm accounts for 40-70% of the total pore volume . Compared with the prior art, the invention has better hydroprocessing performance of inferior raw material oil.

Description

Hydroprocessing method for hydrocarbon oil feedstock with high metal content

technical field

The invention relates to a method for hydrotreating hydrocarbon oil raw materials with high metal content.

Background technique

With the increasing trend of heavy crude oil and the increasing demand for light oil products in social development, it is widely used to produce light oil products or high-quality secondary processing raw materials through hydrotreating of inferior heavy raw materials. In order to improve the product distribution and operation process of secondary processing such as catalytic cracking process, the hydrotreated products are required to have lower impurity content of metals, sulfur, nitrogen and residual carbon. The content of impurities such as metals continues to increase, which requires the hydrotreating process to have better impurity removal capabilities and reaction stability. Improving impurity removal can be achieved by increasing the severity of the hydrotreating reaction, but this also results in a shortened catalyst operating life. Therefore, adopting new catalysts and processing methods is the best choice for producing high-quality secondary processing raw materials.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new hydrotreating method for high-metal low-quality heavy oil with higher impurity removal ability and reaction stability in response to the needs of the existing technology.

The present invention relates to the following:

1. A method for hydrotreating hydrocarbon oil feedstock with high metal content, comprising: under hydrotreating reaction conditions, heavy feedstock oil is sequentially mixed with hydrotreating protection catalyst I, hydrotreating catalyst II and hydrotreating catalyst The catalyst combination of III is contacted, by volume and based on the total amount of the catalyst combination, the content of the hydrogenation protection catalyst I is 5-60%, and the content of the hydrogenation catalyst II is 5-50%, The content of the hydrotreating catalyst III is 10-60%; wherein, the protected hydrotreating catalyst I contains a support and a hydrogenation active metal component supported on the support, wherein the support contains alumina and at least one A kind of additive selected from boron, silicon and fluorine, characterized by mercury porosimetry, the pore volume of the carrier is 0.5-1 ml/g, the specific surface area is 30-150 ^m2 /g, and the most probable pore diameter is 80-300nm , the carrier has a bimodal pore distribution with a diameter of 12-15nm and a diameter of 100-200nm, the pore volume of the pore with a diameter of 12-15nm accounts for 10-22% of the total pore volume, and the pore volume of a pore with a diameter of 100-200nm The pore volume accounts for 40-70% of the total pore volume.

2. The method according to 1, characterized in that, by volume and based on the total amount of the catalyst combination, the content of the hydrotreating protection catalyst I is 10-50%, and the content of the hydrotreating catalyst II The content is 10-40%, and the content of hydrotreating catalyst III is 20-50%; the pore volume of the shaped carrier in the hydrotreating protection catalyst I is 0.5-0.8 ml/g, and the specific surface area is 50- 130 ^m2 /g, the most probable pore diameter is 80-280nm, among which, the pore volume of pores with a diameter of 12-15nm accounts for 10-20% of the total pore volume, and the pore volume of pores with a diameter of 100-200nm accounts for 10% of the total pore volume 45-70%.

3. The method according to 1 or 2, characterized in that, in the hydrotreating protection catalyst I, the content of the auxiliary agent boron and silicon in terms of oxides is 0.1-8% by weight, and the content of fluorine in terms of elements is The content is 0.1-8% by weight.

4. The method according to 3, characterized in that the content of boron and silicon in terms of oxides is 1-6% by weight, and the content of fluorine in terms of elements is 1-6% by weight.

5. The method according to 4, characterized in that the content of boron and silicon in terms of oxides is 1-4% by weight, and the content of fluorine in terms of elements is 1-4% by weight.

6. The method according to 1 or 2, characterized in that the hydrogenation active metal component in the catalyst I is selected from at least one metal component of Group VIII and at least one metal component of Group VIB, with oxides Calculated and based on the catalyst, the content of the Group VIII metal component is greater than 0 to less than or equal to 8% by weight, and the content of the Group VIB metal component is greater than 0 to less than or equal to 10% by weight.

7. The method according to 6, characterized in that the Group VIII metal component is selected from nickel and/or cobalt, and the Group VIB metal component is selected from molybdenum and/or tungsten, calculated as oxides and Based on the catalyst, the content of the Group VIII metal component is 0.2-4% by weight, and the content of the Group VIB metal component is 0.5-8% by weight.

8. The method according to 1, characterized in that the catalyst II contains a carrier, metal components molybdenum, cobalt and nickel, calculated as oxides and based on catalyst II, and the content of molybdenum is 5 to 20 wt. %, the sum of the content of cobalt and nickel is 1-6% by weight, wherein the atomic ratio of cobalt and nickel is 2-4.

9. The method according to 8, characterized in that, in terms of oxides and based on catalyst II, the content of molybdenum in the catalyst II is 8-15% by weight, and the sum of the contents of cobalt and nickel is 1.5-4 % by weight, wherein the atomic ratio of cobalt and nickel is 2.2 to 3.2.

10. The method according to 1, characterized in that the catalyst III contains a support selected from alumina and/or silica-alumina, a hydrogenation activity selected from nickel and/or cobalt, molybdenum and/or tungsten Metal components, containing or not containing one or more additive components selected from fluorine, boron and phosphorus, calculated as oxides and based on catalyst III, the content of nickel and/or cobalt is 1-5 % by weight, the content of molybdenum and/or tungsten is 10-35% by weight, and the content of one or more auxiliary components selected from fluorine, boron and phosphorus in terms of elements is 0-9% by weight.

11. The method according to 10, characterized in that the carrier in the catalyst III is selected from alumina.

12. The method according to 11, characterized in that the pore volume of the alumina is not less than 0.35 ml/g, and the pore volume of pores with a pore diameter of 40-100 angstroms accounts for more than 80% of the total pore volume.

13. The method according to 1, characterized in that the reaction conditions of the hydrogenation treatment reaction are: hydrogen partial pressure 6-20MPa, temperature 300-450°C, liquid hourly volume space velocity 0.1-1h ^-1 , The volume ratio of hydrogen to oil is 600-1500.

14. The method according to 13, characterized in that the reaction conditions of the hydrotreating reaction are: hydrogen partial pressure 10-18MPa, temperature 350-420°C, liquid hourly volume space velocity 0.2-0.6h ^-1 , The volume ratio of hydrogen to oil is 800-1100.

The carrier of catalyst I described in the present invention is characterized by mercury porosimetry, its pore volume is 0.5-1 ml/g, and its specific surface area is 30-150 m / ^g , wherein the pore volume of the 12-15nm pores accounts for 10-22% of the total pore volume, the pore volume of pores with a diameter of 100-200nm accounts for 40-70% of the total pore volume; preferably the pore volume of the shaped carrier is 0.5-0.8 ml/g, and the specific surface area is 50-130 ^m2 /g, wherein the pore volume of pores with a diameter of 12-15nm accounts for 10-20% of the total pore volume, and the pore volume of pores with a diameter of 100-200nm accounts for 45-70% of the total pore volume.

Based on the carrier, the content of the auxiliary agent in the carrier is 0.1-8% by weight, preferably 1-6% by weight, more preferably 1-4% by weight. Among them, boron and silicon are calculated as oxides, and fluorine is calculated as elements.

The hydrogenation active metal component and its content in the catalyst I are usually the hydrogenation active metal component and content commonly used in hydrogenation protection catalysts, for example, selected from at least one Group VIII non-noble metal component and at least one Group VIB metal components. Preferred metal components of group VIII are nickel and/or cobalt, preferred metal components of group VIB are molybdenum and/or tungsten, calculated as oxides and based on the catalyst, the metal of group VIII The content of the group VIB metal component is greater than 0 to less than or equal to 8% by weight, preferably 0.2 to 4% by weight, and the content of the Group VIB metal component is greater than 0 to less than or equal to 10% by weight, preferably 0.5 to 8% by weight.

The preparation method of the carrier described in the hydrogenation protection catalyst I of the present invention comprises mixing a hydrated alumina with a α-alumina and introducing into the mixture a compound containing at least one selected from the group consisting of boron, silicon and fluorine. The compound of the agent, shaped, dried and calcined, the calcined temperature is 750-1000°C, preferably 800-950°C, and the calcined time is 1-10 hours, preferably 2-8 hours, wherein the hydrated alumina on a dry basis The mixing ratio with α-alumina is 20-75:25-80 (wherein, 20-75 refers to the proportion of hydrated alumina per hundred parts of the mixture of hydrated alumina (on a dry basis) and α-alumina The value of the number varies between 20-75, and 25-80 means that in the mixture of per hundred parts of hydrated alumina (on a dry basis) and α-alumina, the value of α-alumina is at 25 -80), preferably 30-70:30-70. The pore volume of the hydrated alumina is 0.9-1.4 ml/g, preferably 0.95-1.3 ml/g, and the specific surface area is 100-350 ^m2 /g, preferably 120-300 ^m2 /g, and most preferably several pores The diameter is 8-30 nm, preferably 10-25 nm.

The method of introducing at least one additive compound selected from boron, silicon, and fluorine into the mixture of hydrated alumina and α-alumina is a conventional method, for example, it may be to directly add a required amount of additives containing the The component compound is mixed in during the aforementioned mixing process of hydrated alumina and α-alumina.

In a specific embodiment of preparing the support, the method of introducing at least one additive compound selected from boron, silicon and fluorine into the mixture of hydrated alumina and α-alumina is to introduce at least one additive compound selected from boron , silicon and fluorine additive compounds are formulated into an aqueous solution, and the aqueous solution is mixed in while the hydrated alumina is mixed with α-alumina or mixed in after the hydrated alumina is mixed with α-alumina, It is then shaped, dried and fired. The compound containing the auxiliary agent is one or more of their water-soluble compounds. For example, one or more of the water-soluble inorganic salts containing the additives.

The α-alumina may be commercially available (commercial α-alumina powder), or may be obtained by calcining hydrated alumina (hydrated alumina powder) at high temperature. Under the conditions sufficient to convert the hydrated alumina into α-alumina, this process can be realized by any existing method, and the present invention is not limited thereto.

The hydrated alumina is selected from arbitrary pore volume of 0.9-1.4 ml/g, preferably 0.95-1.3 ml/g, specific surface of 100-350 ^m2 /g, preferably 120-300 ^m2 /g, most Alumina hydrate with accessible pore diameter of 8-30nm, preferably 10-25nm; preferably hydrated alumina containing pseudo-boehmite. Here, the pore volume, specific surface area and most accessible pore diameter of the hydrated alumina are obtained by BET low-temperature nitrogen adsorption characterization after the hydrated alumina is calcined at 600° C. for 4 hours.

The mixing of the hydrated alumina and α-alumina adopts a conventional method, and the mixing ratio of the hydrated alumina and α-alumina on a dry basis is 20-75:25-80, preferably 30-70:30 -70.

The carrier can be made into various easy-to-handle moldings according to different requirements, such as spherical, honeycomb, bird's nest, tablet or strip (clover, butterfly, cylindrical, etc.). Forming can be carried out by conventional methods. When molding, such as extrusion molding, in order to ensure that the molding is carried out smoothly, water, extrusion aids and/or adhesives, with or without pore-expanding agents, can be added to the mixture, and then extrusion molding, followed by Dried and roasted. The type and amount of the extrusion aid and the peptizing agent are well known to those skilled in the art, for example, the common extrusion aid can be selected from one of squash powder, methyl cellulose, starch, polyvinyl alcohol, polyethanol or several, the peptizer can be inorganic acid and/or organic acid, and the pore-enlarging agent can be one or more of starch, synthetic cellulose, polymeric alcohol and surfactant. Wherein the synthetic cellulose is preferably one or more in hydroxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxycellulose fatty alcohol polyvinyl ether, and the polymeric alcohol is preferably polyethylene glycol, polypropylene alcohol, One or more of polyvinyl alcohol, the surfactant is preferably one of fatty alcohol polyvinyl ether, fatty alcohol amide and its derivatives, acrylic alcohol copolymer and maleic acid copolymer with a molecular weight of 200-10000 or several.

The methods of shaping, drying and firing are conventional methods. Among them, the calcination conditions preferably include a calcination temperature of 750-1000°C and a calcination time of 1-10 hours, and more preferably calcination conditions include a calcination temperature of 800-950°C and a calcination time of 2-8 hours.

The preparation method of the hydrogenation protection catalyst I includes the step of introducing a hydrogenation active metal component onto the carrier, wherein the hydrogenation active metal component is selected from at least one Group VIII non-noble metal and at least one Combinations of Group VIB metals. The metal component of the preferred Group VIB is molybdenum and/or tungsten, in terms of oxides and based on the catalyst, the introduction amount of the metal component of the VIB group makes the content of the metal component of the VIB group in the final catalyst It is greater than 0 to less than or equal to 10% by weight, preferably 0.5 to 8% by weight, and the introduction amount of the Group VIII metal component is such that the content of the Group VIII metal component in the final catalyst is greater than 0 to less than or equal to 8% by weight , preferably 0.2 to 4% by weight.

The introduction of the hydrogenation active metal component to the carrier can be any method known by those skilled in the art, for example, by impregnating the carrier with a solution containing the compound of the hydrogenation active metal component, followed by drying , Roasting or non-roasting steps.

Wherein, the group VIB metal-containing compound is selected from one or more of their soluble compounds. For example, the molybdenum-containing compound can be one or more of molybdenum oxide, molybdate, and paramolybdate, preferably molybdenum oxide, ammonium molybdate, and ammonium paramolybdate; the tungsten-containing compound is selected from tungstate , metatungstate, ethyl metatungstate, one or more of them, ammonium metatungstate and ethyl ammonium metatungstate are preferred.

The compound containing Group VIII metal is selected from one or more of their soluble compounds. For example, the cobalt-containing compound can be one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride, preferably cobalt nitrate and basic cobalt carbonate; the nickel-containing compound can be nickel nitrate, nickel acetate , basic nickel carbonate, nickel chloride in one or more, preferably nickel nitrate, basic nickel carbonate.

According to the present invention, various solvents commonly used in the art can be used to prepare the solution of the compound containing the active ingredient, as long as the compound can be dissolved in the solvent to form a uniform and stable solution. For example: the solvent may be water or an alcohol with 1 to 5 carbon atoms (such as ethanol), preferably water and/or ethanol, more preferably water.

The impregnation method may be various impregnation methods commonly used in the art, such as a pore saturation impregnation method. The present invention has no particular limitation on the impregnation time and the number of impregnation times, as long as the amount of the catalytically active components on the finally obtained catalyst can be ensured to meet specific usage requirements. Generally, the soaking time may be 0.5-12 hours.

In the present invention, the method and conditions for drying the carrier carrying the compound of the hydrogenation active metal component are not particularly limited. Generally, the drying temperature may be 80-350°C, preferably 100-300°C; the drying time may be 0.5-24 hours, preferably 1-12 hours.

When the dried catalyst needs to be calcined, the present invention has no particular limitation on the calcining method and conditions, which may be conventional methods and conditions in the art. Generally, the calcination temperature may be 350-650°C, preferably 400-500°C; the calcination time may be 0.2-12 hours, preferably 1-10 hours. The calcination can be carried out in an oxygen-containing atmosphere or in an inert atmosphere.

In the present invention, the function of the catalyst II is to further remove organic metal impurities, macromolecular species such as asphaltenes and colloids, and part of sulfides in the raw materials.

According to the method provided by the present invention, wherein, under the premise of meeting the requirements of the present invention for the hydrotreating catalyst II, the hydrotreating catalyst II can be commercially available, or can be prepared by any prior art. For example, the catalysts disclosed in 20110276687.3 and 201110039566.1 and their preparation methods are fully suitable for the present invention. The more detailed preparation methods of the above-mentioned catalysts are all described in the above-mentioned patent documents, which are hereby cited as a part of the content of the present invention.

In the present invention, the function of the catalyst III is to further remove impurities such as sulfur and nitrogen that are more difficult to remove in macromolecular compounds such as saturated polycyclic aromatic hydrocarbons, and remove carbon residue in raw oil at the same time to improve product properties. On the premise that it is sufficient to realize the above functions, the present invention has no other restrictions on the catalyst III, that is, the catalyst III can be selected from any catalysts such as hydrorefining and hydrotreating provided by the prior art. They can be commercially available or prepared by any existing method.

Generally, such catalysts usually contain a heat-resistant inorganic oxide support, a hydrogenation active metal component. For example, the catalyst III contains a carrier selected from alumina and/or silica-alumina, a hydrogenation active metal component selected from nickel and/or cobalt, molybdenum and/or tungsten, with or without fluorine , boron and phosphorus, one or more additive components, calculated as oxides and based on catalyst III, the content of nickel and/or cobalt is 1-5% by weight, and the content of molybdenum and/or tungsten is 10-35% by weight, and the content of one or more auxiliary components selected from fluorine, boron and phosphorus in terms of elements is 0-9% by weight.

For example, a hydrorefining catalyst disclosed in ZL97112397 is composed of 1-5% by weight of nickel oxide, 12-35% by weight of tungsten oxide, 1-9% by weight of fluorine, and the rest is alumina, which is made of a or a variety of small-pore alumina and one or more macro-pore alumina according to the weight ratio of 75:25 to 50:50, wherein the small-pore alumina is the pore volume with a pore diameter less than 80 angstroms. Alumina with a pore volume of more than 95%, macroporous alumina is an alumina with a pore volume of pore diameters of 60-600 angstroms accounting for more than 70% of the total pore volume.

ZL00802168 discloses a hydrorefining catalyst containing an alumina support and at least one Group VIB metal and/or at least one Group VIII metal supported on the alumina support. The pore volume of the alumina carrier is not less than 0.35 ml/g, and the pore volume of the pores with a pore diameter of 40-100 angstroms accounts for more than 80% of the total pore volume. It is prepared by a special method.

ZL200310117323 discloses a hydrorefining catalyst, which contains an alumina carrier and molybdenum, nickel and tungsten metal components loaded on the carrier, calculated as oxides and based on the catalyst, the catalyst contains 0.5- 10% by weight of molybdenum, 1-10% by weight of nickel, 12-35% by weight of tungsten and a balanced carrier. The preparation method of the catalyst includes sequentially impregnating and oxidizing the catalyst with a solution containing molybdenum compounds and a solution containing nickel and tungsten compounds. Aluminum carrier, wherein said alumina carrier is dried after being impregnated with a solution containing a molybdenum compound, dried and calcined after being impregnated with a solution containing a nickel and tungsten compound, the drying temperature is 100-300°C, and the drying time is 1 -12 hours, the roasting temperature is 320-500°C, and the roasting time is 1-10 hours.

These catalysts can all be used in the present invention as said catalyst III. The more detailed preparation methods of the above-mentioned catalysts are all described in the above-mentioned patent documents, which are hereby cited as a part of the content of the present invention.

According to the method provided by the present invention, the hydrogenation catalyst I, the hydrogenation catalyst II and the hydrogenation catalyst III can be sequentially loaded in the same reactor layer by layer, and can also be sequentially loaded in several series reaction reactors. device, the present invention is not particularly limited.

According to the method provided by the present invention, wherein, before, after or between the combination of catalysts including hydrotreating catalyst I, hydrotreating catalyst II and hydrotreating catalyst III, any catalyst that helps to improve the Other catalysts or fillers for catalyst combination properties. For example, fillers such as ceramic balls and active supports are added before the hydrodemetallization catalyst I to improve the distribution of raw oil in the reactor. The use of such fillers is well known to those skilled in the art, and will not be repeated here.

According to conventional methods in this field, before use, the hydrotreating catalyst can be presulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 140-370° C. in the presence of hydrogen, such presulfurization It can be vulcanized outside or in-situ, and the active metal components it supports can be converted into metal sulfides.

According to the method provided by the present invention, the reaction conditions of the hydrotreating reaction are conventional conditions for heavy oil hydrotreating, for example, the reaction conditions include: hydrogen partial pressure 6-20MPa, temperature 300-450°C, liquid hour The volume space velocity is 0.1-1.0h ^-1 , the volume ratio of hydrogen to oil is 600-1500, the preferred hydrogen partial pressure is 10-18MPa, the temperature is 350-420℃, the liquid hourly volume space velocity is 0.2-0.6h ^-1 , the hydrogen The oil volume ratio is 800-1100.

According to the method provided by the present invention, it is especially suitable for processing inferior hydrocarbon oil raw materials with high metal content such as iron and calcium, which can be selected from crude oil, vacuum residue, deep wax oil, light deasphalted oil, coker wax oil , low-quality coal tar, etc. one or more.

The weight of the hydrotreated oil obtained according to the method can reach: the content of asphaltene is less than 1.2%, the content of metal Fe+Ca is less than 15 μg/g, the content of metal Ni+V is less than 20 μg/g, and the content of sulfur is 0.5%. Below, the carbon residue content is 6.0% or less.

detailed description

The following examples will further illustrate the present invention.

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

Mercury porosimetry (RIPP149-90) was used to measure the specific surface area, pore volume, and pore distribution of the alumina molding support (Yang Cuiding et al., Petrochemical Analysis Methods, Academy of Sciences Press, 1990, p. 421-423).

The BET low-temperature nitrogen adsorption method (RIPP151-90) was used to measure the specific surface area, pore volume and pore distribution of hydrated alumina (Yang Cuiding et al., Petrochemical Analysis Methods, Academy of Sciences Press, 1990, p. 424-426).

The dry basis measurement method is to take an appropriate amount of sample and roast it at 600°C for 3 hours, then calculate the mass percentage of the sample after roasting and the sample before roasting, which is the dry basis of the sample.

The XRF method (RIPP132-90) was used to determine the content of elements in solid samples (Yang Cuiding et al., Petrochemical Analysis Methods, Academy of Sciences Press, 1990, p. 371-375).

Hydrotreating protection catalyst I among the present invention and preparation method thereof:

Examples 1-5 illustrate the preparation of the carrier used in the catalyst I of the present invention and the preparation method thereof.

Example 1

Weigh 200g of hydrated alumina (commercially purchased from Changling Catalyst Branch, 65% by weight on a dry basis. The pore volume is 1.05 ml/g, the specific surface area is 230 ^m2 /g, and the most probable pore diameter is 20 nm), 70 gram of α-alumina powder (calculated at 1400° C. for 6 hours by the hydrated alumina used in this example), 9 grams of fennel powder and 15 grams of borax were mixed, and the mixture was mixed with a concentration of 4% at room temperature Mix 330 ml of ammonia solution, mix evenly, knead in a twin-screw extruder and extrude with a φ2.0mm cylindrical orifice, after that, dry the wet strip at 120°C for 4 hours and then roast it at 850°C for 2 hours to obtain this product Invention carrier ZI1. The specific surface, probable pore diameter, pore volume, and pore distribution of carrier ZI1 were measured, and the results are shown in Table 1.

Example 2

Weigh 180g dry rubber powder (commercially purchased from Changling Catalyst Branch Company, dry basis is 65% by weight. The pore volume is 1.05 ml/g, the specific surface area is 285 ^m2 /g, and the most probable pore diameter is 20nm), 120 gram of α-alumina powder (commercially purchased from Beijing Shunchuan Environmental Protection Technology Co., Ltd.), 9 grams of safflower powder and 8 grams of boron oxide were mixed, then added 330 milliliters of aqueous solution containing 10 grams of sodium borate, mixed evenly and extruded in a twin-screw Kneading in a bar machine and extruding with a φ2.0mm cylindrical orifice plate, after that, the wet bar was dried at 120°C for 4 hours and then calcined at 850°C for 2 hours to obtain the carrier ZI2 of the present invention. The specific surface, probable pore diameter, pore volume, and pore distribution of carrier ZI2 were measured, and the results are shown in Table 1.

Example 3

Weigh 150g of dry rubber powder (commercially purchased from Yantai Henghui Chemical Co., Ltd., the dry basis is 68% by weight. The pore volume is 1.08 ml/g, the specific surface area is 188 ^m2 /g, and the most probable pore diameter is 22nm), 150 grams of α-alumina powder (commercially purchased from Beijing Shunchuan Environmental Protection Technology Co., Ltd.), 9 grams of scallop powder, 9 grams of methylcellulose and 20 grams of borax were mixed, and then 330 ml of aqueous solution containing 35 grams of ammonium bicarbonate was added , after mixing evenly, shape according to rolling ball molding method to obtain spherical particles with a particle size of 5.5-6.5mm. The wet strip was dried at 120°C for 4 hours and then calcined at 800°C for 2 hours to obtain the carrier ZI3 of the present invention. The specific surface, probable pore diameter, pore volume, and pore distribution of carrier ZI3 were measured, and the results are shown in Table 1.

Example 4

Weigh 260g of dry rubber powder (commercially purchased from Changling Catalyst Branch Company, dry basis is 65% by weight. Pore volume is 1.05 ml/g, specific surface area is 220 ^m2 /g, most probable pore diameter is 20nm), 140 Gram α-alumina powder (same as embodiment 1), 9 gram asparagus powder, 9 gram methyl cellulose and 10 gram magnesium borate mix homogeneously, then add 300 milliliters of 5% ammonia solution containing 10 gram boric acid, mix, Then add 300 milliliters of water, mix evenly, knead in a twin-screw extruder and extrude with a φ2.0mm cylindrical orifice plate, dry the wet strip at 120°C for 4 hours and then bake it at 800°C for 2 hours to obtain the carrier ZI4 of the present invention . The specific surface, probable pore diameter, and pore volume of carrier ZI4 were measured, and the results are shown in Table 1.

Example 5

Weigh 260g of dry rubber powder (commercially purchased from Yantai Henghui Chemical Co., Ltd., the dry basis is 68% by weight. The pore volume is 1.08 ml/g, the specific surface area is 200 ^m2 /g, and the most probable pore diameter is 22nm), 140 grams of α-alumina powder (same as in Example 1), 9 grams of kale powder, and 9 grams of methylcellulose are mixed, then add 300 milliliters of water containing 10 grams of nitric acid, mix well and extrude into strips, and the wet strips are subjected to 120 After drying at ℃ for 4 hours, calcining at 800℃ for 2 hours, the carrier ZI5 of the present invention was obtained. The specific surface, probable pore diameter, and pore volume of carrier ZI5 were measured, and the results are shown in Table 1.

Comparative Examples 1-4 illustrate the preparation of supports for reference catalysts and their preparation methods.

Comparative example 1

Weigh 300 grams of dry rubber powder (commercially purchased from Changling Catalyst Branch, the dry basis is 65% by weight. The pore volume is 0.8 ml/g, the specific surface area is 320 ^m2 /g, and the most probable pore diameter is 10 nm), 9 grams of scallop powder, mixed evenly, added 360 ml of a solution containing 12 grams of nitric acid, mixed and formed, the wet strip was dried at 120°C for 4 hours, and then calcined at 850°C for 2 hours to obtain the carrier DZI1. The specific surface, probable pore diameter, and pore volume of the carrier DZI1 were measured, and the results are shown in Table 1.

Comparative example 2

Weigh 300 grams of dry rubber powder (commercially purchased from Changling Catalyst Branch, the dry basis is 65% by weight. The pore volume is 0.8 ml/g, the specific surface area is 303 ^m2 /g, and the most probable pore diameter is 11 nm), 9 grams of scallop powder, mixed evenly, added 360 ml of a solution containing 12 grams of nitric acid, mixed and formed, the wet strip was dried at 120°C for 4 hours, and then calcined at 950°C for 2 hours to obtain the carrier DZI2. The specific surface, probable pore diameter, and pore volume of the carrier DZI2 were measured, and the results are shown in Table 1.

Comparative example 3

Weigh dry rubber powder (commercially purchased from Changling Catalyst Branch, dry basis is 65% by weight. The pore volume is 0.8 ml/g, the specific surface area is 290 ^m2 /g, and the most probable pore diameter is 11nm) 300 grams, Add 24 grams of carbon black powder and 12 grams of scallop powder and mix, then add 360 milliliters of aqueous solution containing 2.4 grams of phosphoric acid with a concentration of 85% by weight, knead for 15 minutes, and extrude into a Φ1.5mm butterfly bar on a twin-screw extruder , the wet strip was dried at 120°C for 4 hours and then calcined at 850°C for 2 hours to obtain the carrier DZI3. The specific surface, probable pore diameter, and pore volume of the carrier DZI3 were measured, and the results are shown in Table 1.

Comparative example 4

Weigh 300 grams of dry rubber powder (commercially purchased from Changling Catalyst Branch, the dry basis is 65% by weight. The pore volume is 0.65 ml/g, the specific surface area is 288 ^m2 /g, and the most probable pore diameter is 9 nm), 9 grams of turmeric powder and 15 grams of borax were mixed evenly, and then 360 ml of a solution containing 12 grams of potassium nitrate was added to form the mixture. The wet strip was dried at 120°C for 4 hours and then calcined at 950°C for 2 hours to obtain the carrier DZI4. The specific surface, probable pore diameter, and pore volume of the carrier DZI4 were measured, and the results are shown in Table 1.

Table 1

Examples 6-10 are used to illustrate the catalyst I of the present invention and its preparation method. Comparative Examples 5-6 illustrate reference catalysts and their preparation.

Example 6

Take 100 grams of ZI1 as a carrier, impregnate it, dry it and roast it, impregnate it with 97 ml of a solution containing 1.2 g of molybdenum oxide (containing 99.9% MoO ₃ ) and 0.7 g of nickel nitrate (containing 25% NiO) in a saturated impregnation method, and dry it at 120°C for 4 hour, and calcined at 420° C. for 3 hours to obtain the protected catalyst CI1 of the present invention. Wherein, the content of hydrogenation active metal components is listed in Table 2.

Example 7

Take 100 grams of ZI2 as a carrier, impregnate with 96 ml of a solution containing 6.42 g of ammonium molybdate (containing 82% MoO ₃ ) and 4.35 g of nickel nitrate (containing 51% of NiO) in a saturated impregnation method, and dry at 120°C for 4 hours after impregnation. Calcined at 420°C for 3 hours to obtain the protected catalyst CI2 of the present invention. Wherein, the content of hydrogenation active metal components is listed in Table 2.

Example 8

Take 20 grams of ZI3 carrier, impregnate with 25 ml of solution containing 1.2g ammonium molybdate (containing 82% MoO ₃ ) and 2.0g nickel nitrate (containing 25% NiO) in a saturated impregnation method, dry at 120°C for 4 hours after impregnation, and dry at 120°C for 4 hours. Calcined at 420°C for 3 hours to obtain the protected catalyst CI3 of the present invention. Wherein, the content of hydrogenation active metal components is listed in Table 2.

Example 9

Take 20 grams of ZI4 carrier, impregnate with 13 ml of solution containing 0.86g ammonium molybdate (containing 82% MoO ₃ ) and 1.25g nickel nitrate (containing 25% NiO) in a saturated impregnation method, and dry at 120°C for 4 hours after impregnation. Calcined at 420°C for 3 hours to obtain the protected catalyst CI4 of the present invention. Wherein, the content of hydrogenation active metal components is listed in Table 2.

Example 10

Take 20 grams of ZI5 carrier, impregnate with 13 ml of solution containing 1.45 g ammonium molybdate (containing MoO ₃ 82%) and 1.30 g nickel nitrate (containing NiO 25%) in a saturated impregnation method, dry at 120°C for 4 hours after impregnation, and Calcined at 420°C for 3 hours to obtain the protected catalyst CI5 of the present invention. Wherein, the content of hydrogenation active metal components is listed in Table 2.

Comparative Examples 5-6 illustrate reference catalysts and their preparation.

Comparative example 5

Take 20 grams of DZI4 as a carrier, impregnate with 25 ml of a solution containing 1.2 g of ammonium molybdate (containing 82% MoO ₃ ) and 2.0 g of nickel nitrate (containing 25% of NiO) in a saturated impregnation method, and dry at 120°C for 4 hours after impregnation. Calcined at 420°C for 3 hours to obtain the protected catalyst DCI1 of the present invention. Wherein, the content of hydrogenation active metal components is listed in Table 2.

Comparative example 6

Take 20 grams of DZI1 carrier, impregnate with 13 ml of solution containing 0.86g ammonium molybdate (containing 82% MoO ₃ ) and 1.25g nickel nitrate (containing 25% NiO) in a saturated impregnation method, and dry at 120°C for 4 hours after impregnation. Calcined at 420°C for 3 hours to obtain the protected catalyst DCI2 of the present invention. Wherein, the content of hydrogenation active metal components is listed in Table 2.

Table 2

Examples 11-12 illustrate supports suitable for use in the preparation of Hydrotreating Catalyst II and methods for their preparation.

Example 11

The pseudo-boehmite dry rubber powder RPB110 produced by 300 gram Changling Catalyst Branch Company and 10 gram of fenugreek powder are mixed homogeneously, at room temperature this mixture and the concentration of 360 milliliters are 1% nitric acid aqueous solution, mix homogeneously, After continuing to knead on a twin-screw extruder to form a plastic body, extrude into a trefoil-shaped strip of ф1.5 mm, dry the wet strip at 120°C for 3 hours, and then calcinate at 700°C for 3 hours to obtain the carrier ZⅡ1. The specific surface area, pore volume and pore size distribution of ZⅡ1 were measured, and the results are shown in Table 3.

The specific surface area, pore volume and pore size distribution of the carrier were measured by BET low temperature nitrogen adsorption method.

Example 12

Mix 300 grams of pseudo-boehmite dry rubber powder RPB90 (Pseudo-boehmite dry rubber powder RPB90) produced by Changling Catalyst Branch Company and 10 grams of scallop powder, add 330 milliliters of nitric acid aqueous solution with a concentration of 1%, and mix Evenly, continue kneading on a twin-screw extruder to form a plastic body, extrude into a butterfly-shaped strip of ф1.1 mm, dry the wet strip at 110°C for 2 hours, and roast at 600°C for 4 hours to obtain the carrier ZⅡ2. The specific surface area, pore volume and pore size distribution of ZⅡ2 were measured, and the results are shown in Table 3.

table 3

Examples 13-16 illustrate Catalyst II used by the present invention and its preparation.

Example 13

Take 1200 grams of the carrier ZII prepared in Example 11, impregnate it with 500 milliliters of ammonium molybdate, nickel nitrate, and cobalt nitrate mixed solution containing MoO3120 g/L, NiO8 g/L, CoO20 g/L for 1 hour, filter and bake at 120 ° C. After drying for 2 hours and calcining at 450°C for 4 hours, catalyst CII1 was obtained. Based on the total weight of the catalyst, the content of molybdenum oxide, cobalt oxide and nickel oxide in the catalyst CII1 was measured by X-ray fluorescence spectrometer, and the measurement results are shown in Table 4. (All instruments are 3271 X-ray fluorescence spectrometers from Japan Rigaku Electric Industry Co., Ltd. For specific methods, see Petrochemical Analysis Method RIPP133-90)

Example 14

Get the carrier ZⅡ2200 grams that embodiment 12 prepares, with 220 milliliters containing MoO3172 g/liter, NiO9 g/liter, CoO32 g/liter molybdenum oxide, basic nickel carbonate, basic cobalt carbonate mixed solution impregnation 2 hours, at 120 ℃ drying for 2 hours, and 500 ℃ calcining for 2 hours to obtain catalyst CII2. The content of molybdenum oxide, cobalt oxide and nickel oxide in the catalyst CII2 was measured in the same manner as in Example 3, and the results are shown in Table 4.

Example 15

Get the carrier ZⅡ2200 grams that embodiment 12 prepares, with 200 milliliters containing MoO3122 grams/liter, NiO9 grams/liter, the mixed solution of CoO18 grams/liter molybdenum oxide, basic nickel carbonate, basic cobalt carbonate impregnates 1 hour, at 120 It was dried at ℃ for 2 hours and calcined at 480℃ for 4 hours to obtain catalyst CII3. The contents of molybdenum oxide, nickel oxide and cobalt oxide in the catalyst CII3 were determined in the same manner as in Example 3, and the results are shown in Table 4.

Example 16

Take 1200 grams of the carrier ZII prepared in Example 11, impregnate it with 500 milliliters of cobalt nitrate mixed solution containing 12 grams/liter of CoO for 1 hour, dry it at 110°C for 3 hours after filtering, roast at 350°C for 2 hours, and use 200 milliliters of cobalt nitrate solution containing 392 grams/liter of MoO liter, NiO7 g/liter molybdenum oxide, basic nickel carbonate mixed solution impregnated for 1 hour, dried at 120°C for 2 hours, and calcined at 480°C for 4 hours to obtain catalyst CII4. The content of molybdenum oxide, nickel oxide and cobalt oxide in the catalyst CII4 was determined in the same manner as in Example 3, and the results are shown in Table 4.

Table 4

Examples 17-21 illustrate the effect of the method provided by the present invention in hydrotreating the mixed feedstock of residual oil and coal tar. Comparative Examples 7-8 illustrate the effect of the reference method for hydrotreating the residue feedstock.

The catalyst was evaluated in a 500ml fixed-bed reactor with Fe+Ca content of 79ppm, Ni+V content of 85ppm, sulfur content of 3.7%, and residual carbon of 11.5%.

The content of iron, calcium, nickel and vanadium in the oil sample was measured by an inductively coupled plasma emission spectrometer (ICP-AES) (the instrument used was the PE-5300 plasma light meter of the American PE company, and the specific method is shown in the petrochemical analysis method RIPP124-90 ).

The sulfur content in the oil sample was determined by the coulometric method (see the petrochemical analysis method RIPP62-90 for the specific method).

The residual carbon content in the oil sample was determined by the trace method (see the petrochemical analysis method RIPP149-90 for the specific method).

Hydrotreating Catalyst III:

Hydrotreating catalyst III-1 is prepared according to Example 6 in patent ZL97112397.7, and its composition is 2.3% by weight of nickel oxide, 22.0% by weight of tungsten oxide, 4% by weight of fluorine, and the rest is alumina.

Hydrotreating catalyst III-2 is prepared according to Example 37 in patent ZL00802168.6, and its composition is 2.6% by weight of nickel oxide, 23.6% by weight of molybdenum oxide, 2.3% by weight of fluorine, and the rest is alumina.

Hydrotreating catalyst III-3 was prepared according to Example 3 in patent ZL200310117323.0, and its composition was 2.1% by weight of nickel oxide, 2.5% by weight of molybdenum oxide, 25.4% by weight of tungsten oxide, and the rest was alumina.

Catalyst usage ratio and process conditions are listed in Table 5, and product properties are listed in Table 6 after running for 1000 hours.

Comparative example 7

The catalyst used was a combination of DCI1, CII1, and CIII1. The volume ratio and process conditions of each catalyst were listed in Table 5. After 1000 hours of operation, samples were taken and analyzed, and the results were listed in Table 6.

Comparative example 8

The catalyst used was a combination of DCI2, CII2, and CIII2. The volume ratio and process conditions of each catalyst were listed in Table 5. After 1000 hours of operation, samples were taken and analyzed, and the results were listed in Table 6.

table 5

Table 6

It can be seen that the metal, sulfur, carbon residue and other impurity contents of the hydrotreated product after the method provided by the invention has been operated for 1000 hours are significantly lower than the reference method.

Claims (14)

1. A method for hydrotreating a hydrocarbon oil feedstock with high metal content, comprising, under hydrotreating reaction conditions, sequentially reacting heavy feedstock oil with a hydrotreating protection catalyst I, a hydrotreating catalyst II and a hydrotreating catalyst The catalyst combination of III is contacted by volume and based on the total amount of the catalyst combination, the content of the hydrotreating protection catalyst I is 5-60%, and the content of the hydrotreating catalyst II is 5-50%, The content of the hydrogenation catalyst III is 10-60%; wherein, the hydrogenation protection catalyst I contains a support and a hydrogenation active metal component supported on the support, wherein the support contains alumina and at least one A kind of additive selected from boron, silicon and fluorine, characterized by mercury porosimetry, the pore volume of the carrier is 0.5-1 ml/g, the specific surface area is 30-150 ^m2 /g, and the most probable pore diameter is 80-300nm , the carrier has a bimodal pore distribution with a diameter of 12-15nm and a diameter of 100-200nm, the pore volume of the pore with a diameter of 12-15nm accounts for 10-22% of the total pore volume, The pore volume accounts for 40-70% of the total pore volume. 2. The method according to claim 1, characterized in that, by volume and based on the total amount of the catalyst combination, the content of the hydrotreating protection catalyst I is 10-50%, and the hydrotreating catalyst The content of II is 10-40%, the content of hydrogenation catalyst III is 20-50%; the pore volume of the carrier in the hydrogenation protection catalyst I is 0.5-0.8 ml/g, and the specific surface area is 50 -130 ^m2 /g, the most probable pore diameter is 80-280nm, wherein the pore volume of pores with a diameter of 12-15nm accounts for 10-20% of the total pore volume, and the pore volume of pores with a diameter of 100-200nm accounts for the total pore volume 45-70% of. 3. The method according to claim 1 or 2, characterized in that, in the hydrotreating protection catalyst I, the content of the auxiliary agent boron and silicon in terms of oxides is 0.1-8% by weight, in terms of elements The fluorine content is 0.1-8% by weight. 4. The method according to claim 3, characterized in that the content of the additives boron and silicon in terms of oxides is 1-6% by weight, and the content of fluorine in terms of elements is 1-6% by weight. 5 . The method according to claim 4 , characterized in that the content of boron and silicon in terms of oxides is 1-4% by weight, and the content of fluorine in terms of elements is 1-4% by weight. 6. The method according to claim 1 or 2, characterized in that, the hydrogenation active metal component in the catalyst I is selected from at least one metal component of Group VIII and at least one metal component of Group VIB, with In terms of oxides and based on the catalyst I, the content of the Group VIII metal component is greater than 0 to less than or equal to 8% by weight, and the content of the Group VIB metal component is greater than 0 to less than or equal to 10% by weight. 7. The method according to claim 6, wherein the Group VIII metal component is selected from nickel and/or cobalt, the VIB Group metal component is selected from molybdenum and/or tungsten, and oxide Calculated and based on the catalyst I, the content of the Group VIII metal component is 0.2-4% by weight, and the content of the Group VIB metal component is 0.5-8% by weight. 8. The method according to claim 1, characterized in that, the catalyst II contains a carrier, metal components molybdenum, cobalt and nickel, in terms of oxides and based on the catalyst II, the content of the molybdenum is 5-5. 20% by weight, the sum of the content of cobalt and nickel is 1-6% by weight, wherein the atomic ratio of cobalt and nickel is 2-4. 9. The method according to claim 8, characterized in that, in terms of oxides and based on catalyst II, the content of molybdenum in the catalyst II is 8 to 15% by weight, and the sum of the content of cobalt and nickel is 1.5 ~4% by weight, wherein the atomic ratio of cobalt and nickel is 2.2~3.2. 10. The method according to claim 1, characterized in that, the catalyst III contains a carrier selected from alumina and/or silica-alumina, an additive selected from nickel and/or cobalt, molybdenum and/or tungsten Hydrogen-active metal components, containing or not containing one or more auxiliary components selected from fluorine, boron and phosphorus, calculated as oxides and based on catalyst III, the content of nickel and/or cobalt is 1 -5% by weight, the content of molybdenum and/or tungsten is 10-35% by weight, and the content of one or more auxiliary components selected from fluorine, boron and phosphorus in terms of elements is 0-9% by weight. 11. The method according to claim 10, characterized in that the carrier in the catalyst III is selected from alumina. 12. The method according to claim 11, characterized in that, the pore volume of the carrier alumina in the catalyst III is not less than 0.35 ml/g, and the pore diameter is 40 to 100 angstroms. More than 80%. 13. The method according to claim 1, wherein the reaction conditions of the hydroprocessing reaction are: hydrogen partial pressure 6-20MPa, temperature 300-450°C, liquid hourly volume space velocity 0.1-1h ^{- 1} , The volume ratio of hydrogen to oil is 600-1500. 14. The method according to claim 13, characterized in that, the reaction conditions of the hydroprocessing reaction are: hydrogen partial pressure 10-18MPa, temperature 350-420°C, liquid hourly volume space velocity 0.2-0.6h ^-1 , the volume ratio of hydrogen to oil is 800-1100.