CN104437519B - Residuum hydrotreatment catalyst, and preparation and application thereof - Google Patents

Abstract

A residual oil hydrotreating catalyst and its preparation and application, the catalyst contains an alumina carrier and a hydrogenation active metal component, wherein the hydrogenation active metal component is selected from at least one Group VIII metal component and at least one Group VIB metal component, calculated as an oxide and based on the catalyst, the content of the Group VIII metal component is greater than 3 to less than or equal to 10% by weight, and the content of the Group VIB metal component is greater than 10 to Less than or equal to 40% by weight, the carrier has a bimodal pore structure, characterized by mercury intrusion porosimetry, the pore volume of the carrier is 0.6-1.4 ml/g, the specific surface area is 80-400 m2/g, and the diameter is 5-400 m2/g. The pore volume of the 20nm pores accounts for 30-60% of the total pore volume, and the pore volume of the 100-300nm pores accounts for 15-45% of the total pore volume. Compared with the prior art, the catalyst provided by the invention has better performance of hydrotreating carbon residue removal when used in residual oil hydrotreating.

Description

A catalyst for residual oil hydrotreating and its preparation and application

technical field

The invention relates to a heavy oil hydrotreating catalyst and its preparation and application.

Background technique

As the contradiction between heavy and low-quality crude oil and the diversification and light-weight of petrochemical products worldwide becomes increasingly acute, the combined process of residual oil hydrogenation and catalytic cracking is becoming more and more important. The main purpose of residual oil hydrogenation technology is to provide qualified raw materials for catalytic cracking (RFCC). As RFCC feed, the properties of residual oil hydrogenation products, especially the metal, sulfur, nitrogen and carbon residue values, have an important impact on the catalytic cracking process. Among them, the carbon residue value of residual oil hydrogenation products is more important to the impact of catalytic cracking. The carbon residue value of heavy oil represents the coking trend of high boiling point components in the processing process. an important indicator. It is generally desired that the carbon residue content of residual oil hydrogenation products used as RFCC feedstock be less than 6% [5]. Raw materials with high residual carbon value, high coke and oil slurry yields during RFCC processing, will greatly affect the operational stability and product distribution of RFCC units. Reducing the residual carbon value of the oil produced by the residual oil hydrogenation unit will help improve the properties of catalytic cracking raw materials, improve product distribution, and help improve the economic benefits of the residual oil hydrogenation and catalytic cracking unit.

The catalyst support provides paths and spaces for the diffusion of reactant molecules and the deposition of metal impurities, and also provides the necessary dispersion and support surfaces for the loading of active components. Different reactions require catalysts with different diffusion properties and active specific surfaces. After the residual oil passes through the protective agent and demetallization agent bed, the raw material entering the carbon removal and desulfurization agent bed contains a large amount of polycyclic aromatic hydrocarbons and other compounds. When the pore size of the catalyst is small, the mass transfer resistance is relatively large. On the other hand, since the material contacted by the carbon removal agent still contains a certain amount of metals, the deposition of carbon deposits and metal sulfides may also cause the blockage of the catalyst pores, restricting the diffusion of reactant molecules into the pores of the catalyst. active center. A large number of studies have shown that improper pore structure is one of the important factors leading to the deactivation of residue hydrotreating catalysts. The pore size distribution is of great significance to the catalyst performance. Macroporous catalysts are beneficial to the removal of macromolecular carbon residue precursors such as colloids and asphaltenes, but the pore size of the catalyst is negatively correlated with the specific surface area, that is, the catalyst with a large average pore size has a small specific surface area. Therefore, in order to take into account this property, the catalyst needs to have a reasonable pore distribution.

The disadvantage of existing heavy oil hydrogenation catalysts is that their S, N removal rates, heavy metal removal rates and asphaltenes removal rates cannot be well matched. For example, catalysts with high metal removal activity often S, N removal rate and carbon residue removal rate are not high. The reasons for such problems are complex. The first is the raw material. The components in the residual oil are characterized by large molecular weight, complex structure, low saturation (high aromaticity), and high S and N contents. In the prior art, catalysts having apertures suitable for such reactions are protection catalysts and demetallization catalysts, such as:

CN1267537C discloses a hydrodemetallization catalyst with lower carbon deposition and higher activity and its preparation method.

CN1796500A discloses a residual oil hydrogenation demetallization catalyst, which is composed of a carrier with double pores and molybdenum and/or tungsten and cobalt and/or nickel metal components loaded on the carrier. The preparation method of the carrier used in the catalyst includes mixing a precursor of alumina and a nitrogen-containing compound other than acid, shaping and calcining.

CN1233795C discloses a heavy oil fixed-bed hydrotreating catalyst and a preparation method thereof.

However, the common problem of the catalysts provided by the prior art is that the removal rate of carbon residue is low.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new catalyst with better hydrogenation carbon residue removal performance, the preparation method and application of the catalyst.

The content involved in the present invention includes:

1. A residue hydrotreating catalyst comprising an alumina carrier and a hydrogenation active metal component, wherein the hydrogenation active metal component is selected from at least one Group VIII metal component and at least one VIB Group metal components, calculated as oxides and based on catalysts, the content of the group VIII metal components is greater than 3 to 10% by weight, and the content of the Group VIB metal components is greater than 10 to 40% by weight, The carrier has a bimodal pore structure, which is characterized by mercury intrusion porosimetry. The pore volume of the carrier is 0.6-1.4 ml/g, the specific surface area is 80-400 ^m2 /g, and the pore volume of pores with a diameter of 5-20 nm accounts for 30-60% of the total pore volume, and the pore volume of pores with a diameter of 100-300nm accounts for 15-45% of the total pore volume.

2. according to the described catalyst of 1, it is characterized in that, the pore volume of described carrier is 0.7-1.3 milliliter/gram, and specific surface area is 100-300 meter / gram, and diameter is that the pore volume of ^5-20nm hole accounts for total hole The volume of pores with a diameter of 100-300nm accounts for 20-40% of the total pore volume.

3. The catalyst according to 1, wherein the Group VIII metal component is selected from cobalt and/or nickel, and the VIB Group metal component is selected from molybdenum and/or tungsten, in terms of oxide and catalyst As a basis, the content of the Group VIII metal component is 3-6% by weight, and the content of the Group VIB metal component is greater than 11 to less than or equal to 30% by weight.

4. The method for preparing the catalyst according to 1, comprising preparing a carrier and loading a hydrogenation active metal component on the carrier, wherein the preparation of the carrier includes mixing alumina hydrate PA and PB containing pseudo-boehmite with A modified PC of hydrated alumina containing pseudoboehmite is mixed, shaped, dried and calcined, wherein the weight mixing ratio of PA, PB and PC is 20-60:20-50:5-50 , the κ value of PC is 0 to less than or equal to 0.9, said κ=DI ₂ /DI ₁ , DI ₁ is the acid peptization index of alumina hydrate before PC modification, and DI ₂ is the acid peptization index of PC .

5. The method according to 4, characterized in that the weight mixing ratio of PA, PB and PC is 30-50:35-50:10-30.

6. The method according to 4, wherein the k value of the PC is 0 to less than or equal to 0.6.

7. according to the method described in 4 or 5, it is characterized in that, the pore volume of the hydrated alumina PA containing pseudo-boehmite is 0.75-1 ml/g, and the specific surface is 200-450 m/ ^g , The most possible pore diameter is 3-10nm; the pore volume of the hydrated alumina PB containing pseudoboehmite is 0.9-1.4 ml/g, the specific surface is 100-350 ^m2 /g, and the most likely pore diameter is greater than 10 to less than or equal to 30nm.

8. according to the method described in 7, it is characterized in that, the pore volume of the hydrated alumina PA containing pseudo-boehmite is 0.80-0.95 ml/g, and the specific surface is 200-400 ^m2 /g, the most possible The pore diameter is 5-10nm; the pore volume of the hydrated alumina PB containing pseudoboehmite is 0.95-1.3 ml/g, the specific surface area is 120-300 ^m2 /g, and the most possible pore diameter is greater than 10 to Less than or equal to 25nm.

9. The method according to any one of 4, 5 or 6, wherein the PC is 80-300 mesh particles.

10. The method according to 9, characterized in that the PC is 100-200 mesh particles.

11. The method according to 4, wherein the drying conditions include: the temperature is 40-350°C, and the time is 1-24 hours, and the roasting conditions include: the temperature is greater than 500 to less than or equal to 1200°C , the time is 1-8 hours.

12. The method according to 11, wherein the drying conditions include: the temperature is 100-200°C, and the time is 2-12 hours, and the roasting conditions include: the temperature is greater than 800 to less than or equal to 1000°C , The roasting time is 2-6 hours.

13. The method according to 4, wherein one of the methods for modifying the alumina hydrate containing pseudo-boehmite to PC is to form and dry the alumina hydrate containing pseudo-boehmite, Then all or part of it is ground and sieved, and the drying conditions include: the temperature is 40-350 ° C, and the time is 1-24 hours; the second method is to roast the molded product obtained in the first method, and the roasting temperature is greater than 350 to less than or equal to 1400 °C, the roasting time is 1-8 hours, and then all or part of it is ground and sieved; the third method is to flash dry the hydrated alumina containing pseudo-boehmite, and the flash-dry temperature is greater than 150 to less than or equal to 1400°C, and the flash-drying time is 0.05-1 hour; the fourth method is obtained by mixing one or more of the modified products obtained by the first method, the second method and the third method.

14. The method according to 13, characterized in that the drying conditions in the first method include: the temperature is 100-200°C, and the time is 2-12 hours; the calcination temperature in the second method is 500-1200°C , the calcination time is 0.1-6 hours; the flash-drying temperature in method 3 is 200-1000° C., and the flash-drying time is 0.1-0.5 hours.

15. The method according to 13, characterized in that the PC is 80-300 mesh particles in the modified product of alumina hydrate containing pseudoboehmite.

16. The method according to 15, characterized in that the PC is 100-200 mesh particles in the modified product of alumina hydrate containing pseudoboehmite.

17. The method according to 4, characterized in that, the method of loading the hydrogenation active metal component on the carrier is an impregnation method, comprising preparing a solution containing a hydrogenation active metal compound and impregnating the carrier with the solution, and then carrying out Drying, calcined or not calcined, said hydrogenation active metal component is selected from at least one metal component of Group VIB and at least one metal component of Group VIII, calculated as oxide and based on catalyst, so The concentration of the hydrogenation active metal-containing compound in the solution and the amount of the solution make the content of the metal component of Group VIB in the final catalyst greater than 10 to 40% by weight, and the metal of Group VIII The content of the component is greater than 3 to less than or equal to 10% by weight; the drying conditions include: the temperature is 100-250°C, and the time is 1-10 hours; the roasting conditions include: the temperature is 360-500°C, and the time is 1-10 hours. 10 hours.

18. The method according to 17, characterized in that, the metal component of the VIB group is selected from molybdenum and/or tungsten, and the metal component of the VIII group is selected from cobalt and/or nickel, calculated as oxides and Based on the catalyst, the concentration of the hydrogenation active metal-containing compound in the solution and the amount of the solution make the content of the metal component of Group VIB in the final catalyst greater than 11 to less than or equal to 30% by weight. The content of the metal component of Group VIII is 3-6% by weight; the drying conditions include: the temperature is 100-140°C, and the time is 1-6 hours; the roasting conditions include: the temperature is 360-450°C, and the time is 2-6 hours.

19. The application of the catalyst according to any one of claims 1-3 in residual oil hydrotreating.

According to the catalyst provided by the present invention, depending on different requirements, the carrier can be made into various easy-to-handle shapes, such as spherical, honeycomb, bird's nest, tablet or strip (clover, butterfly, cylindrical, etc.). The molding can be carried out by conventional methods, for example, one method or a combination of several methods among ball rolling, sheet pressing and extrusion molding. 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.

In the present invention, the acid peptization index DI refers to the hydrated alumina containing pseudoboehmite and the modified alumina hydrate containing pseudoboehmite after adding nitric acid at a certain acid-aluminum ratio, in a certain reaction Percentage of hydrated alumina containing pseudoboehmite peptized within the time, calculated as Al ₂ O ₃ , DI=(1-W ₂ /W ₁ )×100%, W ₁ and W ₂ are respectively Hydrated alumina of diaspore before and after reaction with _acid by weight in terms of _Al2O3 .

The determination of DI includes: (1) Determination of the ignited base (also called dry base) content of hydrated alumina containing pseudo-boehmite (the ignited base content refers to roasting quantitative pseudo-boehmite at 600°C for 4 hours , the ratio of the weight after burning to the weight before burning, expressed as a percentage), is counted as a; (2) Use an analytical balance to weigh W ₀ grams of hydrated alumina containing pseudo-boehmite, and the amount of W ₀ meets the requirement of Al ₂ O The W ₁ of ₃ is 6 grams (W ₁ /a=W ₀ ), weigh W grams of deionized water, W=40.0-W ₀ , and mix the weighed alumina hydrate containing pseudo-boehmite and Add deionized water into the beaker and mix; (3) use a 20mL pipette to pipette 20mL of dilute nitric acid solution with a concentration of 0.74N, add the acid solution into the beaker of step (2), and react for 8 minutes under stirring; (3) Centrifuge the reacted slurry in a centrifuge, put the precipitate into a weighed crucible, then dry it at 125°C for 4 hours, bake it in a muffle furnace at 850°C for 3 hours, and weigh The weight of the burnt sample is W ₂ grams; (5) is calculated according to the formula DI=(1-W ₂ /W ₁ )×100%.

Under the premise that the final carrier is sufficient to meet the requirements of the present invention, the present invention has no special requirements for the hydrated alumina PA and PB containing pseudo-boehmite, which can be pseudo-boehmite prepared by any prior art, or It may be a mixture of pseudo-boehmite and other hydrated alumina, and the other hydrated alumina is selected from one or more of monohydrate alumina, trihydrate alumina and amorphous hydrate alumina.

In a specific embodiment, the hydrated alumina PA containing pseudoboehmite preferably has a pore volume of 0.75-1 ml/g, a specific surface of 200-450 ^m2 /g, and a most likely pore diameter of 3-10 nm , further preferably the pore volume is 0.80-0.95 ml/g, the specific surface is 200-400 ^m2 /g, and the most possible pore diameter is 5-10nm; the preferred pore volume of the hydrated alumina PB containing pseudo-boehmite is 0.9-1.4 ml/g, the specific surface is 100-350 ^m2 /g, the most probable pore diameter is greater than 10 to less than or equal to 30 nm, more preferably the pore volume is 0.95-1.3 ml/g, and the specific surface is 120-300 ^m2 /g, the most probable pore diameter is greater than 10 to less than or equal to 25nm.

In the present invention, the pore volume, specific surface area and most probable pore diameter of the hydrated alumina containing pseudo-boehmite are determined by BET Nitrogen adsorption was characterized.

In a further preferred embodiment, as characterized by X-ray diffraction, the pseudo-boehmite content in the pseudo-boehmite-containing alumina hydrates PA and PB is not less than 50%, more preferably not less than 60%.

The inventors of the present invention surprisingly found that the modified product PC is obtained by heat-treating alumina hydrate containing pseudo-boehmite. Compared with the original hydrated alumina containing pseudo-boehmite, the peptization of the modified product PC The index changes, and after molding this modification with PA and PB, drying and calcination, the obtained support has a clear bimodal pore distribution. Especially after the 80-300 mesh particles, preferably 100-200 mesh particles are mixed with PA and PB, dried and calcined, the pore distribution of each unimodal in the obtained bimodal carrier is particularly concentrated. Here, the 80-300 mesh particles, preferably 100-200 mesh particles mean that the modified product has been sieved (including the step of crushing or grinding if necessary), and the sieved material (undersize) meets the 80-300 mesh Particles, preferably 100-200 mesh particles, account for a percentage (by weight) of not less than 60% of the total, more preferably not less than 70%. The hydrated alumina containing pseudo-boehmite here can be pseudo-boehmite prepared by any prior art, or a mixture of pseudo-boehmite and other hydrated aluminas, and the other hydrated aluminas One or more selected from alumina monohydrate, alumina trihydrate and amorphous hydrated alumina. In a preferred embodiment, the PC is a modified product of PA and/or PB.

In the present invention, the weight mixing ratio of PA, PB and PC refers to the ratio of the parts by weight of PA, PB and PC in the mixture of PA, PB and PC per hundred parts. Among them, PA:PB:PC is preferably 20-60:20-50:5-50, more preferably 30-50:35-50:10-30.

Among the present invention, described PC can obtain conveniently by following method:

Hereinafter, a method for obtaining PC will be described using the aforementioned PA and PB as starting materials.

⑴Based on drying to obtain PC, including the tailings produced by drying during the preparation of conventional alumina carriers by forming hydrated alumina PA and/or PB containing pseudoboehmite according to conventional methods, for example: in extrusion molding , the tailings (customarily called dry waste) produced by the drying and shaping process of the strip-shaped moldings, the tailings are ground and sieved to obtain PC.

(2) Obtained on the basis of roasting, including the tailings (customarily called roasting waste) produced by roasting during the preparation of conventional alumina carriers from hydrated alumina PA and/or PB containing pseudoboehmite according to conventional methods, For example, in rolling ball molding, the tailings produced by the spherical particles during the roasting process are ground and sieved to obtain PC; or directly obtained by flashing PA and/or PB. And/or when PB is flash-dried, the flash-dry time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour.

(3) Obtained based on the mixture of two or more of the modified PCs obtained by the aforementioned method. When using the mixing method to obtain C, there is no limit to the mixing ratio of the modified PC obtained by the aforementioned methods.

According to the catalyst provided by the present invention, wherein, the hydrogenation active metal component is preferably a group VIII metal component of cobalt and/or nickel, and a VIB group metal component is molybdenum and/or tungsten, calculated as an oxide and as a catalyst Based on this, the content of the Group VIII metal component is preferably greater than 3 to less than or equal to 10% by weight, more preferably 3-6% by weight, and the content of the Group VIB metal component is preferably greater than 10 to less than or equal to 40% by weight, More preferably, it is more than 11 to 30% by weight or less.

On the premise that it is sufficient to load the hydrogenation active metal component on the carrier, the present invention has no special limitation on the loading method, and the preferred method is the impregnation method, including the impregnation of preparing the compound containing the metal solution, which is then used to impregnate the carrier. The impregnation method is a conventional method, for example, it may be impregnation with excess liquid or pore saturation method. The metal component compound selected from group VIB is selected from one or more of the soluble compounds in them, such as one or more of molybdenum oxide, molybdate, paramolybdate, preferably among them Molybdenum oxide, ammonium molybdate, ammonium paramolybdate; one or more of tungstate, metatungstate, ethyl metatungstate, preferably ammonium metatungstate, ethyl ammonium metatungstate . The compound containing metal components selected from Group VIII is selected from one or more of their soluble compounds, such as cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and cobalt soluble complexes One or more, preferably cobalt nitrate, basic cobalt carbonate; one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel soluble complexes, preferably nickel nitrate , Basic nickel carbonate.

The catalyst provided by the present invention may also contain any additional components that do not affect the performance of the catalyst provided by the present invention or can improve the catalytic performance of the catalyst provided by the present invention. If it may contain additional components such as phosphorus, the content of the additional components is not more than 10% by weight, preferably 0.1-4% by weight, based on the oxide and the catalyst.

When the catalyst also contains additional components such as phosphorus, the introduction method of the additional components can be any method, such as directly mixing the compound containing the phosphorus and other components with the pseudo-boehmite Mixing, molding and roasting; it may be that the compound containing the phosphorus and other components and the compound containing the hydrogenation active metal component are formulated into a mixed solution and then impregnated with the carrier; it may also be that the compound containing the phosphorus and other components is separately After preparing the solution, the carrier is impregnated and fired. When additional components such as phosphorus and hydrogenation active metals are respectively introduced into the carrier, it is preferred to firstly impregnate the carrier with a solution containing the compound of the additional components and roast, and then use a solution containing the compound of the hydrogenation active metal Dipping. Wherein, the calcination temperature is 400-600°C, preferably 420-500°C, and the calcination time is 2-6 hours, preferably 3-6 hours.

According to the residual oil hydrotreating method provided by the present invention, the reaction conditions for the hydrotreating of the hydrocarbon oil are not particularly limited. In a preferred embodiment, the reaction conditions for the hydrotreating are as follows: a reaction temperature of 300-550 °C, more preferably 330-480 °C, hydrogen partial pressure 4-20 MPa, more preferably 6-18 MPa, volume space velocity 0.1-3.0 h ^-1 , more preferably 0.15-2 h ^-1 , hydrogen-oil volume ratio 200 -2500, more preferably 300-2000.

The device for the hydrogenation reaction can be carried out in any reactor sufficient to make the feedstock oil contact with the catalyst under the hydrotreating reaction conditions, for example, in the fixed bed reactor, moving bed reactor or carried out in an ebullating bed reactor.

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 supported by it can be converted into metal sulfide components.

The catalyst provided by the invention can be used alone or in combination with other catalysts. The catalyst is especially suitable for hydrotreating heavy oil, especially inferior residue oil, so as to provide qualified raw material oil for subsequent processes (such as catalytic cracking process). Compared with the prior art, the catalyst provided by the invention has better performance of hydrotreating carbon residue removal when used in residual oil hydrotreating.

detailed description

The following examples will further illustrate the present invention, but should not be construed as a limitation of the present invention.

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

The pseudo-boehmite used in the following examples includes:

PA-1: Dry rubber powder produced by Changling Catalyst Branch (pore volume is 0.9 ml/g, specific surface is 280 ^m2 /g, and the most probable pore diameter is 8.5nm. The dry basis is 73%, of which the pseudo-thin water The content of gibbsite is 68%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 34.6).

PA-2: Dry rubber powder produced by Zibo Qimao Catalyst Co., Ltd. (the pore volume is 0.9 ml/g, the specific surface is 290 ^m2 /g, the most probable pore diameter is 8.3nm. The dry basis is 73%, of which the pseudo-thin water The content of gibbsite is 68%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 33.2).

PB-1: Dry rubber powder produced by Changling Catalyst Branch (pore volume is 1.2 ml/g, specific surface is 280 ^m2 /g, and the most probable pore diameter is 15.8nm. Dry basis is 73%, of which pseudo-thin water The content of gibbsite is 68%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 15.8).

PB-2: Dry rubber powder produced by Yantai Henghui Chemical Co., Ltd. (pore volume is 1.1 ml/g, specific surface is 260 ^m2 /g, and the diameter of most pores is 12nm. Dry basis is 71%, of which pseudo-thin water The content of gibbsite is 67%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 17.2).

Examples 1-8 illustrate the PC and its preparation method of the present invention.

Example 1

Weigh 1000 grams of PA-1, then add 1000 milliliters of an aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. Dry the wet strips at 120°C for 4 hours to obtain dry strips, shape the dry strips, sieve, grind and sieve the dry strip materials (generally called industrial dry strip waste) with a length of less than 2mm, and take 100-200 Mesh sieving to obtain the modified PC-A1 of PA-1. See Table 1 for the k value of PC-A1.

Example 2

Weigh 1000 grams of PA-1, then add 1000 milliliters of an aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. The wet strips were dried at 120°C for 4 hours, and roasted at 800°C for 4 hours to obtain the carrier. The carrier strips were shaped and sieved, and the carrier strip materials (generally called industrial carrier waste) with a length of less than 2mm were ground, sieved, and collected. Among them, sieve with 100-200 meshes to obtain the modified product PC-A2 of PA-1. See Table 1 for the k value of PC-A2.

Example 3

Weigh 1000g of PA-2, and flash dry at 400°C for 6 minutes to obtain PC-A3, a modified product of PA-2. See Table 1 for the k value of PC-A3.

Example 4

Each 200 grams of PC-A1 obtained in Example 1 and PC-A3 obtained in Example 3 were evenly mixed to obtain the modified PC-A4 of PA-1 and PA-2. See Table 1 for the k value of PC-A4. .

Example 5

Weigh 1000 grams of PB-1, then add 1440 milliliters of aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. The wet strips were dried at 120°C for 4 hours, and roasted at 1200°C for 4 hours to obtain the carrier. The carrier strips were shaped and sieved, and the carrier strip materials (generally called industrial carrier waste) with a length of less than 2mm were ground, sieved, and collected. Among them, 100-200 mesh sieve to obtain the modified product PC-B1 of PB-1. See Table 1 for the k value of PC-B1.

Example 6

Weigh 1000 g of PB-2 and flash dry at 650°C for 10 minutes to obtain PC-B2, a modified product of PB-2. See Table 1 for the k value of PC-B2.

Example 7

Weigh 1000 grams of PB-2, then add 1440 milliliters of aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. Dry the wet strips at 120°C for 4 hours to obtain dry strips, shape the dry strips, sieve, grind and sieve the dry strip materials (generally called industrial dry strip waste) with a length of less than 2mm, and take 100-200 Mesh sieving to obtain the modified product PC-B3 of PB-2. See Table 1 for the k value of PC-B3.

Example 8

Each 200 grams of PC-B1 obtained in Example 5 and PC-B2 obtained in Example 6 were evenly mixed to obtain the modified product PC-B4 of PB-1 and PB-2. See Table 1 for the k value of PC-B4.

Table 1

Example raw material DI k 1 PC-A1 10.0 0.29 2 PC-A2 0.9 0.02 3 PC-A3 3.6 0.11 4 PC-A4 6.7 0.20 5 PC-B1 0 0 6 PC-B2 2.1 0.12 7 PC-B3 5.3 0.31 8 PC-B4 1.0 0.06

Examples 9-16 illustrate the preparation method of the bimodal pore support provided by the present invention. Comparative Examples 1-5 illustrate the preparation of conventional catalyst supports.

Example 9

Take by weighing each 400 grams of PA-1 and PB-1, after mixing evenly with 200 grams of raw material PC-A2 obtained in Example 2, add 1300 milliliters of aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. On the screw extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120° C. for 4 hours to obtain a shaped product, which was calcined at 900° C. for 3 hours to obtain a carrier Z1. The properties of carrier Z1 are listed in Table 2.

Example 10

Take by weighing 300 grams of PA-2, 200 grams of PB-2, after mixing evenly with the 500 grams of raw material PC-B2 that embodiment 6 makes, add the aqueous solution 1300 milliliters containing 10 milliliters of nitric acid Tianjin Chemical Reagent No. On the screw extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 900° C. for 3 hours to obtain a carrier Z2. The properties of carrier Z2 are listed in Table 2.

Example 11

Take by weighing 500 grams of PA-2, 300 grams of PB-2, after mixing evenly with the 200 grams of raw material PC-B4 that embodiment 8 makes, add the aqueous solution 1300 milliliters containing 10 milliliters of nitric acid Tianjin Chemical Reagent No. On the screw extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 950° C. for 3 hours to obtain a carrier Z3. The properties of carrier Z3 are listed in Table 2.

Comparative example 1

Weigh 500 grams of PA-2 and 500 grams of PB-2, mix them evenly, add 10 milliliters of aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. strip. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 900°C for 3 hours to obtain a carrier DZ1. The properties of vector DZ1 are listed in Table 2.

Comparative example 2

Weigh 400 grams of PA-1, 600 grams of PB-1, mix evenly, add 10 milliliters of aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. strip. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 950°C for 3 hours to obtain the carrier DZ2. The properties of vector DZ2 are listed in Table 2.

Example 12

Take by weighing 250 gram PA-1, 500 gram PB-1, after the 100 gram raw material PC-A1 that makes with embodiment 1 and the 150 gram raw material PC-B3 that embodiment 7 make evenly mix, add nitric acid (Tianjin chemical 1300 milliliters of aqueous solution of 10 milliliters of the product of the reagent factory No. 3, extruded into a butterfly bar with an outer diameter of φ1.4 mm on a twin-screw extruder. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 1000° C. for 3 hours to obtain a carrier Z4. The properties of carrier Z4 are listed in Table 2.

Example 13

Take by weighing 350 gram PA-2, 350 gram PB-2, after the 150 gram raw material PC-B1 that the 150 gram raw material PC-A3 that embodiment 3 makes and embodiment 5 make evenly mix, add the Tianjin chemical reagent that contains nitric acid The third factory product) 1440 milliliters of aqueous solution of 10 milliliters, extrude into the butterfly bar of external diameter φ 1.4mm on twin-screw extruder. The wet strip was dried at 120° C. for 4 hours to obtain a shaped product, which was calcined at 1000° C. for 3 hours to obtain a carrier Z5. The properties of vector Z5 are listed in Table 2.

Example 14

Take by weighing 200 grams of PA-1, 600 grams of PB-1, after mixing evenly with the 200 grams of raw material PC-B1 that embodiment 5 makes, add the aqueous solution 1440 milliliters containing 10 milliliters of nitric acid Tianjin Chemical Reagent No. On the screw extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 850°C for 3 hours to obtain a carrier Z6. The properties of carrier Z6 are listed in Table 2.

Example 15

Take by weighing 200 grams of PA-1, 600 grams of PB-1, after mixing evenly with the 200 grams of raw material PC-A4 that embodiment 4 makes, add the aqueous solution 1440 milliliters containing 10 milliliters of nitric acid Tianjin Chemical Reagent No. On the screw extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 850° C. for 3 hours to obtain a carrier Z7. The properties of vector Z76 are listed in Table 2.

Example 16

Take by weighing 200 grams of PA-1, 600 grams of PB-1, after mixing evenly with the 200 grams of raw material PC-A2 that embodiment 2 makes, add the aqueous solution 1440 milliliters that contains 10 milliliters of nitric acid (Tianjin Chemical Reagent No. On the screw extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 850° C. for 3 hours to obtain a carrier Z8. The properties of carrier Z8 are listed in Table 2.

Comparative example 3

According to the method provided in Example 7 of the patent CN1782031A, the butterfly bar with an outer diameter of φ1.4mm is extruded on a plunger extruder. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 900°C for 3 hours to obtain the carrier DZ3. The properties of vector DZ3 are listed in Table 2.

Comparative example 4

According to the method provided in Example 1 of the patent CN1120971A, the butterfly bar with an outer diameter of φ1.4mm is extruded on a plunger extruder. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 1000°C for 3 hours to obtain a carrier DZ3. The properties of vector DZ3 are listed in Table 2.

Comparative example 5

Weigh 200 grams of PA-1, 800 grams of PB-2, add 1300 milliliters of an aqueous solution containing 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 1000°C for 3 hours to obtain the carrier DZ5. The properties of vector DZ5 are listed in Table 2.

Table 2

From the results in Table 2, it can be seen that compared with the conventional method, the alumina support prepared by the method provided by the present invention has an obvious bimodal pore structure.

Examples 17-20 illustrate the catalysts provided by the present invention and methods for their preparation.

Among them, the content of active metal components in the catalyst was measured by X-ray fluorescence spectrometer (all instruments are X-ray fluorescence spectrometer 3271 of Japan Rigaku Electric Industry Co., Ltd., for specific methods, see petrochemical analysis method RIPP133-90).

Example 17

Take 200 grams of carrier Z1, impregnate it with 210 milliliters of MoO ₃ 174.8 g/L, CoO4 2.2 g/L mixed solution of molybdenum oxide and basic cobalt carbonate for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours , to obtain catalyst C1. The contents of molybdenum oxide and cobalt oxide in catalyst C1 are listed in Table 3.

Comparative example 6

Take 200 grams of carrier DZ1, impregnate with 180 ml of molybdenum oxide and basic cobalt carbonate mixed solution containing MoO ₃ 203.9 g/L, CoO 49.2 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours , to obtain catalyst DC1. The contents of molybdenum oxide and cobalt oxide in catalyst DC1 are listed in Table 3.

Example 18

Take 200 g carrier Z2, impregnate it with 200 ml molybdenum oxide and basic nickel carbonate mixed solution containing MoO ₃ 124.3 g/l, NiO2 9.6 g/l for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours, Catalyst C2 is obtained. The contents of molybdenum oxide and nickel oxide in catalyst C2 are listed in Table 3.

Comparative example 7

Take 200 g carrier DZ3, impregnate it with 180 ml molybdenum oxide and basic nickel carbonate mixed solution containing MoO ₃ 138.1 g/l, NiO3 2.9 g/l for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours, Catalyst DC2 is obtained. The contents of molybdenum oxide and nickel oxide in catalyst DC2 are listed in Table 3.

Example 19

Take 200 grams of carrier Z3, impregnate it with 205 milliliters of MoO ₃ 179.1 g/L, NiO4 3.2 g/L ammonium molybdate and nickel nitrate mixed solution for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours. Catalyst C3 is obtained. The contents of molybdenum oxide and nickel oxide in catalyst C3 are listed in Table 3.

Comparative example 8

Take 200 grams of carrier DZ4, impregnate with 180 milliliters of molybdenum oxide and basic nickel carbonate mixed solution containing MoO ₃ 203.9 g/L, NiO 49.2 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours , to obtain catalyst DC3. The contents of molybdenum oxide and nickel oxide in catalyst DC3 are listed in Table 3.

Example 20

Take 200 grams of carrier Z8, impregnate with 200 milliliters of molybdenum oxide and basic cobalt carbonate mixed solution containing MoO ₃ 209.1 g/L, CoO5 2.3 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours , to obtain catalyst C4. The contents of molybdenum oxide and cobalt oxide in catalyst C5 are listed in Table 3.

Comparative example 9

Take 200 grams of carrier DZ5, impregnate with 200 milliliters of molybdenum oxide and basic cobalt carbonate mixed solution containing MoO ₃ 209.1 g/L, CoO5 2.3 g/L for 1 hour, dry at 120°C for 2 hours, and bake at 420°C for 3 hours , to obtain catalyst DC4. The contents of molybdenum oxide and cobalt oxide in catalyst DC4 are listed in Table 3.

table 3

Examples 21-24

Examples 21-24 illustrate the residual carbon desulfurization performance of the catalyst provided by the invention.

Catalysts C1, C2, C3 and C4 were broken into particles with a diameter of 2-3 mm and loaded into the reactor. The reaction conditions are: reaction temperature 380°C, hydrogen partial pressure 14 MPa, feedstock oil: feedstock oil with a nickel content of 15.6ppm, a vanadium content of 38.2ppm, a sulfur content of 3.3%, a nitrogen content of 0.24%, and a residual carbon content of 10.7 % Maoming Shaqing VRDS.

Product analysis: Determination of residual carbon content in treated oil by using petroleum product carbon residual test method (the instrument used is MCRT-160 trace carbon residual tester from American ALCOR Company, see GB/T17144 for specific methods). Use the coulometric method to determine the sulfur content (see the petrochemical analysis method RIPP62-90 for the specific method).

Calculate the total removal rate of impurities according to the following formula:

The activity data of each catalyst are shown in Table 4.

Comparative example 10-13

The carbon residue removal rate and desulfurization rate of catalysts DC1, DC2, DC3 and DC4 were evaluated according to the method of Examples 21-24, and the results are shown in Table 4.

Table 4

Example Catalyst number Carbon removal rate/% Desulfurization rate/% twenty one C1 48.4 82.0 Comparative example 10 DC1 43.9 81.8 twenty two C2 50.2 79.8 Comparative example 11 DC2 44.7 78.6 twenty three C3 51.9 81.1 Comparative example 12 DC3 45.3 78.9 twenty four C4 49.4 83.0 Comparative example 13 DC4 46.0 83.0

As can be seen from the results in Table 4, the carbon removal activity and desulfurization activity of the catalyst provided by the present invention are significantly better than existing catalysts in the process of residue hydrotreating, indicating that the catalyst of the present invention is more suitable for the processing of inferior residues .

Claims (18)

1. a kind of catalyst for hydrotreatment of residual oil, containing alumina support and hydrogenation active metals component, wherein, described hydrogenation is lived Property metal component be selected from least one metal component of group VIII and at least one vib metals component, in terms of oxide and with On the basis of catalyst, the content of described VIII race's metal component is more than 3 to less than or equal to 10 weight %, metal component of group VIB Content is more than 10 to less than or equal to 40 weight %, and described carrier has structure of double peak holes, is characterized with mercury injection method, the hole of described carrier Hold for 0.6-1.4 ml/g, specific surface area is 80-400 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 30- of total pore volume 60%, the pore volume in a diameter of 100-300nm hole accounts for the 15-45% of total pore volume.

2. catalyst according to claim 1 it is characterised in that described carrier pore volume be 0.7-1.3 ml/g, than Surface area is 100-300 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-50% of total pore volume, a diameter of 100-300nm The pore volume in hole accounts for the 20-40% of total pore volume.

3. catalyst according to claim 1 is it is characterised in that described metal component of group VIII is selected from cobalt and/or nickel, and the Group vib metal component is selected from molybdenum and/or tungsten, is counted and on the basis of catalyst by oxide, the content of described VIII race's metal component For 3-6 weight %, the content of metal component of group VIB is more than 11 to less than or equal to 30 weight %.

4. the preparation method of catalyst according to claim 1, including preparing carrier and load hydrogenation activity on this carrier Metal component, wherein, the preparation of described carrier is included by the hydrated alumina PA containing boehmite with containing the thin water aluminum of plan The hydrated alumina PB of stone is mixed with a kind of modifier PC of the hydrated alumina containing boehmite, molding, drying roasting Burn, wherein, the pore volume of the described hydrated alumina PA containing boehmite is 0.75-1 ml/g, and specific surface is 200-450 Rice²/ gram, most probable bore dia 3-10nm；The pore volume of the described hydrated alumina PB containing boehmite is 0.9-1.4 milli Rise/gram, specific surface is 100-350 rice²/ gram, most probable bore dia is more than 10 to less than or equal to 30nm；Described PA, PB and PC's Mixing ratio by weight is 20-60：20-50：The κ value of 5-50, PC for 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁Change for PC The sour peptization index of the hydrated alumina before property, DI₂Sour peptization index for described PC.

5. method according to claim 4 is it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50：35- 50：10-30.

6. method according to claim 4 it is characterised in that described PC κ value for 0 to less than or equal to 0.6.

7. the method according to claim 4 or 5 is it is characterised in that the described hydrated alumina PA containing boehmite Pore volume be 0.80-0.95 ml/g, specific surface be 200-400 rice²/ gram, most probable bore dia 5-10nm；Described containing plan The pore volume of the hydrated alumina PB of boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice²/ gram, most probable hole With diameter greater than 10 to less than or equal to 25nm.

8. the method according to claim 4,5 or 6 any one is it is characterised in that described PC is the granule of 80-300 mesh Thing.

9. method according to claim 8 is it is characterised in that described PC is the particulate matter of 100-200 mesh.

10. method according to claim 4 is it is characterised in that the condition of described drying includes：Temperature is 40-350 DEG C, Time is 1-24 hour, and the condition of described roasting includes：Temperature is that the time is that 1-8 is little more than 500 to less than or equal to 1200 DEG C When.

11. methods according to claim 10 are it is characterised in that the condition of described drying includes：Temperature is 100-200 DEG C, the time is 2-12 hour, and the condition of described roasting includes：Temperature is to less than or equal to 1000 DEG C more than 800, and roasting time is 2-6 hour.

12. methods according to claim 4 are it is characterised in that be modified as the hydrated alumina containing boehmite One of method of PC is by the described hydrated alumina molding containing boehmite, drying, completely or partially enters it afterwards Row grinds, screening, and the condition of described drying includes：Temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are by method One of the article shaped roasting that obtains, sintering temperature is that roasting time is 1-8 hour, afterwards more than 350 to less than or equal to 1400 DEG C It is completely or partially ground, sieves；The three of method are that the hydrated alumina containing boehmite dodges dry, the dry temperature of sudden strain of a muscle Degree is that flash-off time is 0.05-1 hour more than 150 to less than or equal to 1400 DEG C；The four of method be by one of method, method it Two and method three modifiers obtaining in several be mixed to get.

13. methods according to claim 12 are it is characterised in that the condition of drying in one of methods described includes：Temperature Spend for 100-200 DEG C, the time is 2-12 hour；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1- 0.5 hour.

14. methods according to claim 12 are it is characterised in that described PC is the hydrated alumina containing boehmite Modifier in 80-300 mesh particulate matter.

15. methods according to claim 14 are it is characterised in that described PC is the hydrated alumina containing boehmite Modifier in 100-200 mesh particulate matter.

16. methods according to claim 4 it is characterised in that described in supported on carriers hydrogenation active metals component Method is infusion process, and the solution including the compound prepared containing hydrogenation active metals simultaneously uses this solution impregnating carrier, carries out afterwards Drying, roasting or not roasting, described hydrogenation active metals group is selected from metal component and at least one of at least one vib The metal component of the VIIIth race, is counted and on the basis of catalyst by oxide, and the described compound containing hydrogenation active metals is described The consumption of the concentration of solution and described solution makes the content of the metal component of the vib in final catalyst be more than 10 to being less than Equal to 40 weight %, the content of the metal component of described VIIIth race is more than 3 to less than or equal to 10 weight %；Described drying condition bag Include：Temperature is 100-250 DEG C, and the time is 1-10 hour；Described roasting condition includes：Temperature is 360-500 DEG C, and the time is 1-10 Hour.

17. methods according to claim 16 it is characterised in that described vib metal component be selected from molybdenum and/or Tungsten, the metal component of the VIIIth race is selected from cobalt and/or nickel, is counted and on the basis of catalyst by oxide, described golden containing hydrogenation activity The compound belonging to makes the metal component of the vib in final catalyst in the concentration of described solution and the consumption of described solution Content is more than 11 to less than or equal to 30 weight %, and the content of the metal component of the VIIIth race is 3-6 weight %；Described drying condition bag Include：Temperature is 100-140 DEG C, and the time is 1-6 hour；Described roasting condition includes：Temperature is 360-450 DEG C, and the time is that 2-6 is little When.

Application in residual hydrocracking for the catalyst described in any one in 18. claim 1-3.