A residue oil hydrogenation catalyst and its preparation method and application

Abstract

The present invention provides a residual oil hydrogenation catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) calcining an aluminum source at 250-400°C to obtain an alumina carrier; (2) impregnating the alumina carrier in an impregnation solution containing a group VIB and group VIII metal compound, drying, and calcining again at 500-700°C to obtain the residual oil hydrogenation catalyst product. The present invention uses a preparation method of first calcining at a low temperature to obtain a carrier and then calcining at a high temperature to obtain a catalyst, and anchors and disperses active metal oxide components into the pores of the carrier alumina, so that the catalyst pore volume utilization rate exceeds 88%, thereby maximizing the utilization rate of active metals.

Description

Technical Field

[0001] The invention relates to the field of hydrogenation catalysts, and in particular to a residual oil hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] The lightening and high-quality improvement of heavy oil is an important task that needs to be solved urgently. Residue oil hydroprocessing technology is an effective means to solve the above problems. Among the existing residue oil hydroprocessing technologies, fixed bed residue oil hydroprocessing technology is the most mature and widely used. Fixed bed residue oil hydroprocessing catalysts usually adopt a graded system, and the loading ratio (volume ratio) of upstream protective agent and demetallizing agent to downstream desulfurization and decarbonizing agent is about 1:1. Compared with the upstream protective agent and demetallizing agent, the metal deposition on the downstream desulfurization and decarbonizing agent (HDS, HDMCR) is low, far from its metal capacity, the catalyst specific surface area and pore volume utilization are not high, and the active metal is not fully utilized. During the use of residue oil hydrodesulfurization and decarbonizing catalysts, carbon deposition and metal deposition will generally occur, resulting in a gradual decrease in activity, and eventually the pore openings will be blocked, and the activity in the remaining pores cannot be utilized, and the catalyst pore volume utilization is less than 76%. Existing preparation technologies have adopted measures such as improving the catalyst pore concentration, increasing the dispersion of active metals, or the gradient distribution of active metals, which have improved the utilization rate of active metals to a certain extent, but the improvement is not obvious enough and the utilization rate of active metals still needs to be improved.

[0003] Chinese patent CN101927169B discloses a hydrogenation catalyst with a gradient-increasing concentration of active metal components and a preparation method thereof, wherein Al2O3 or Al2O3 containing SiO2, TiO2, and ZrO2 is used as a carrier, VIB and / or VIII group metal compounds and deionized water or ammonia water are mixed to form a metal impregnation solution, and a hydrogenation catalyst is prepared by a saturated impregnation method; a relatively dilute VIB and / or VIII group metal solution or deionized water is prepared, and during the carrier impregnation process, a relatively concentrated metal solution is gradually added to saturate the carrier; or metal solutions of different concentrations are prepared, and the metal impregnation solution is impregnated on the carrier in order from low to high concentrations, and the catalyst is obtained after drying and roasting. The catalyst has good desulfurization, denitrification, and carbon residue removal activity and stability, is simple to prepare, and has a low manufacturing cost. It is suitable for the field of heavy oil hydrogenation, but the pore volume and metal utilization rate of the catalyst in this patent are not significantly improved.

[0004] Chinese patent CN103998128A discloses a self-activating hydroprocessing catalyst and method, wherein the catalyst is formed into particles by grinding a mixture of inorganic oxide powder, molybdenum trioxide powder and nickel compound together, and then calcining the particles, and the obtained calcined particles have a pore size distribution that contributes to the unique properties of the catalyst. When contacting a heavy residue feed with high nickel, vanadium and sulfur concentrations under appropriate treatment conditions, the autocatalytic catalyst is activated, and the catalyst exhibits good activity stability. However, the catalyst is prepared by a full kneading method, the active metal dispersion is low, the pores are not smooth, and the activity is not fully exerted.

[0005] Chinese patent CN105983413B discloses a method for preparing a highly active residue oil hydrogenation catalyst, comprising the following steps: using Al2O3 as a carrier, mixing rare earth compounds, active metal compounds, and deionized water or ammonia water to prepare a metal impregnation solution, preparing a hydrogenation catalyst by a saturated impregnation method, and then drying at 70-160°C for 1-9h, and then roasting in air at 280-650°C for 1-7h, and finally obtaining a catalyst in which rare earth metal oxides and active metal oxides are distributed on the catalyst surface at intervals, wherein the active metal compound is selected from at least one of the group consisting of molybdenum compounds, tungsten compounds, nickel compounds, and cobalt compounds, and the active metal oxide is selected from at least one of the group consisting of MoO3, WO3, CoO, and NiO. This patent improves the dispersion of active metals, but the catalyst pore volume and metal utilization are not significantly improved. Summary of the invention

[0006] In order to solve the above technical problems, the purpose of the present invention is to provide a residue oil hydrogenation catalyst and its preparation method and application. The present invention adopts a preparation method of first low-temperature calcination to obtain a carrier and then high-temperature calcination to obtain a catalyst, so that the active metal oxide component is anchored and dispersed in the pores of the carrier alumina, so that the catalyst pore volume utilization rate exceeds 88%, thereby maximizing the utilization rate of the active metal.

[0007] To achieve the above object, the present invention provides a method for preparing a residue oil hydrogenation catalyst, comprising the following steps:

[0008] (1) calcining an aluminum source at 250-400° C. to obtain an alumina carrier;

[0009] (2) The alumina carrier is impregnated in an impregnation solution containing Group VIB and Group VIII metal compounds, dried, and then calcined again at 500-700° C. to obtain the finished residue oil hydrogenation catalyst.

[0010] According to a specific embodiment of the present invention, preferably, in the above-mentioned preparation method, the aluminum source is pseudo-boehmite dry glue powder, and the method for preparing the alumina carrier comprises: mixing the pseudo-boehmite dry glue powder, sesbania powder and a peptizing agent, kneading and then extruding into strips, and then drying and calcining at 250-400°C to obtain the alumina carrier.

[0011] According to a specific embodiment of the present invention, preferably, in the above preparation method, the mass ratio of the pseudo-boehmite dry rubber powder to the sesbania powder is 100:(1-8).

[0012] According to a specific embodiment of the present invention, preferably, in the above preparation method, the peptizing agent is acetic acid.

[0013] According to a specific embodiment of the present invention, preferably, in the above preparation method, the impregnation solution further contains an acid or a base.

[0014] According to a specific embodiment of the present invention, preferably, in the above preparation method, the acid is selected from phosphoric acid.

[0015] According to a specific embodiment of the present invention, preferably, in the above preparation method, the base is selected from ammonia water.

[0016] According to a specific embodiment of the present invention, preferably, in the above preparation method, the calcination temperature in step (1) is 300-380°C.

[0017] According to a specific embodiment of the present invention, preferably, in the above preparation method, the calcination time in step (1) is 1-8 hours, more preferably 2-5 hours.

[0018] According to a specific embodiment of the present invention, preferably, in the above preparation method, the re-calcination temperature in step (2) is 550-620°C.

[0019] According to a specific embodiment of the present invention, preferably, in the above preparation method, the re-roasting time in step (2) is 1-7h.

[0020] According to a specific embodiment of the present invention, preferably, in the above preparation method, the impregnation adopts a saturated impregnation method; the above preparation method also includes homogenizing the impregnated aluminum oxide.

[0021] The present invention also provides a residual oil hydrogenation catalyst obtained by the above preparation method, which comprises an alumina carrier and an active metal oxide, wherein the active metal oxide comprises Group VIB and Group VIII metal oxides;

[0022] Based on the total weight of the catalyst, the content of the Group VIB metal oxide is 4-12%, and the content of the Group VIII metal oxide is 0.5-5%.

[0023] According to a specific embodiment of the present invention, preferably, in the above-mentioned residue hydrogenation catalyst, the Group VIB metal is selected from tungsten and / or molybdenum.

[0024] According to a specific embodiment of the present invention, preferably, in the above-mentioned residue oil hydrogenation catalyst, the Group VIII metal is selected from cobalt and / or nickel.

[0025] According to a specific embodiment of the present invention, preferably, in the above-mentioned residue oil hydrogenation catalyst, the content of the active metal oxide is 1-16% based on the total weight of the catalyst.

[0026] According to a specific embodiment of the present invention, preferably, in the above-mentioned residue oil hydrogenation catalyst, the content of the Group VIII metal oxide is 0.9-4.5%.

[0027] According to a specific embodiment of the present invention, preferably, the pore volume of the above-mentioned residue oil hydrogenation catalyst is 0.3-2.0 ml / g, more preferably 0.40-1.5 ml / g.

[0028] According to a specific embodiment of the present invention, preferably, the specific surface area of ​​the above-mentioned residue oil hydrogenation catalyst is 70-300m 2 / g, more preferably 110-270m 2 / g.

[0029] The present invention also provides an application of the residue oil hydrogenation catalyst obtained by the preparation method in residue oil hydrogenation.

[0030] According to a specific embodiment of the present invention, preferably, in the above application, the residue oil hydrogenation catalyst is used for hydrodesulfurization and / or hydrodecarbonization of residue oil.

[0031] During the use of residual oil hydrodesulfurization and carbon removal catalyst, carbon deposition and metal deposition will generally occur, resulting in a gradual decrease in activity, and eventually the pores will be blocked, and the activity in the remaining pores cannot be utilized, and the catalyst pore volume utilization rate is less than 76%. Existing preparation technologies have taken measures such as increasing the concentration of catalyst pores, increasing the dispersion of active metals, or gradient distribution of active metals, which have improved the utilization rate of active metals to a certain extent, but there has not yet been a technology with an active metal utilization rate exceeding 88%.

[0032] Compared with the prior art, the residue oil hydrogenation catalyst of the present invention and its preparation method and application have the following beneficial effects:

[0033] The present invention uses a preparation method to prepare a carrier by first calcining at a low temperature and then calcining at a high temperature to prepare a catalyst, so that the active metal oxide components are anchored and dispersed in the pores of the carrier alumina, so that the active metal components are distributed in a proper position. Figure 1As shown, an effective deposition space is provided for the carbon deposits generated by the residual oil hydrogenation reaction, which will not accumulate too quickly to block the catalyst pores, thereby maximizing the catalyst pore volume and metal activity utilization, thereby improving the catalyst's ability to remove impurities such as sulfur and residual carbon. The pore volume utilization of the residual oil hydrogenation catalyst of the present invention exceeds 88%, thereby maximizing the utilization of active metals and obtaining ultra-high catalyst activity stability. In addition, the residual oil hydrogenation catalyst of the present invention has a simple preparation process, low cost, and good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a schematic diagram of the distribution of active metal pores in the residue oil hydrogenation catalyst of the present invention. DETAILED DESCRIPTION

[0035] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0036] The macroporous pseudo-boehmite dry glue powder used in the specific embodiment of the present invention is produced by Yantai Henghui Chemical Co., Ltd.

[0037] Example 1

[0038] This embodiment provides a residue oil hydrogenation catalyst, and the preparation method thereof comprises the following steps:

[0039] (1) Preparation of alumina carrier

[0040] 300 g of macroporous pseudo-boehmite dry rubber powder (dry basis content 70 wt%) is added with 6 g of sesbania powder and mixed evenly. 52 g of 3.0 wt% acetic acid solution is added to the above materials and kneaded into a plastic body. It is then extruded into four-leaf clover strips with a diameter of 1.1 mm on a forward extrusion single-screw extruder, dried at 110°C for 3 h, and then calcined at 300°C for 5 h to obtain an alumina carrier.

[0041] (2) Preparation of residue oil hydrogenation catalyst

[0042] Weigh 100g of the above-mentioned alumina carrier, and use the saturated impregnation method to spray a solution prepared by 11g of ammonium molybdate (containing 82wt% of MoO3), 8g of nickel nitrate (containing 25.2wt% of NiO), and 8g of ammonia water (concentration 18wt%). After homogenization in a spraying equipment for 15min, dry at 110°C for 2h, and calcine at 580°C for 3h to obtain a residual oil hydrogenation catalyst, recorded as catalyst C1, which contains 8.0wt% of MoO3 and 1.8wt% of NiO.

[0043] Example 2

[0044] This embodiment provides a residue oil hydrogenation catalyst, and the preparation method thereof comprises the following steps:

[0045] (1) Preparation of alumina carrier

[0046] Weigh 300 g of macroporous pseudo-boehmite dry rubber powder (dry basis content 70 wt%), add 10 g of sesbania powder, mix evenly, add 52 g of 3.0 wt% acetic acid solution to the above materials, knead into a plastic body, and then extrude into four-leaf clover strips with a diameter of 1.1 mm on a forward extrusion single-screw extruder, dry at 120°C for 2 h, and then calcine at 380°C for 2.5 h to obtain an alumina carrier.

[0047] (2) Preparation of residue oil hydrogenation catalyst

[0048] Weigh 100g of the above-mentioned alumina carrier, and use the saturation impregnation method to spray a solution prepared by 14.6g of molybdenum trioxide powder (containing MoO3 99.9wt%), 6.7g of basic nickel carbonate (containing NiO 51.4wt%), and 7.6g of phosphoric acid (containing H3PO4 85wt%). After homogenization in a spraying equipment for 15min, dry at 110°C for 2h, and calcine at 620°C for 3h to obtain a residual oil hydrogenation catalyst, recorded as catalyst C2, which contains 11.9wt% of MoO3, 2.8wt% of NiO and 3.9wt% of P2O5.

[0049] Example 3

[0050] This embodiment provides a residue oil hydrogenation catalyst, and the preparation method thereof comprises the following steps:

[0051] (1) Preparation of alumina carrier

[0052] Weigh 300 g of macroporous pseudo-boehmite dry rubber powder (dry basis content 70 wt%) produced by Yantai Henghui Chemical Co., Ltd., add 6 g of sesbania powder, mix evenly, add 52 g of acetic acid solution with a concentration of 3.0 wt% to the above materials, knead into a plastic body, and then extrude into four-leaf clover strips with a diameter of 1.1 mm on a forward extrusion single-screw extruder, dry at 120°C for 2 h, and then calcine at 350°C for 3 h to obtain an alumina carrier.

[0053] (2) Preparation of residue oil hydrogenation catalyst

[0054] Weigh 100g of the above-mentioned alumina carrier, and use the saturated impregnation method to spray a solution prepared by 14.5g of ammonium molybdate (containing 82wt% of MoO3) and 14g of cobalt nitrate (containing 25.2wt% of CoO). After homogenization in a spraying equipment for 15min, dry at 100°C for 4h, and calcine at 620°C for 4h to obtain a residual oil hydrogenation catalyst, recorded as catalyst C3, which contains 10.3wt% of MoO3 and 3.1wt% of CoO.

[0055] Example 4

[0056] This embodiment provides a residue oil hydrogenation catalyst, and the preparation method thereof comprises the following steps:

[0057] (1) Preparation of alumina carrier

[0058] Weigh 300 g of macroporous pseudo-boehmite dry rubber powder (dry basis content 70 wt%), add 12 g of sesbania powder, mix evenly, add 52 g of acetic acid solution with a concentration of 3.0 wt% to the above materials, knead into a plastic body, and then extrude into four-leaf clover strips with a diameter of 1.1 mm on a forward extrusion single-screw extruder, dry at 100°C for 5 h, and then calcine at 290°C for 6 h to obtain an alumina carrier.

[0059] (2) Preparation of residue oil hydrogenation catalyst

[0060] Weigh 100g of the above-mentioned alumina carrier, and use the saturated impregnation method to spray a solution prepared by 6.7g of ammonium metatungstate (containing WO382wt%) and 8.7g of cobalt nitrate (containing CoO 25.2wt%). After homogenization in the spraying equipment for 15min, dry at 100°C for 3h, and calcine at 550°C for 6h to obtain a residual oil hydrogenation catalyst, recorded as catalyst C4, which contains 5.2wt% of WO3 and 1.2wt% of CoO.

[0061] Comparative Example 1

[0062] This comparative example adopts a conventional catalyst preparation method to provide a catalyst, and its preparation method is the same as that of Example 1, except that the two calcination temperatures are different from those of Example 1. In this comparative example, the carrier is calcined at a high temperature, and the catalyst is calcined at a medium or low temperature. Specifically, the following steps are included:

[0063] (1) Preparation of alumina carrier

[0064] Weigh 300g of macroporous pseudo-boehmite dry rubber powder (dry basis content 70wt%) produced by Yantai Henghui Chemical Co., Ltd., add 6g of sesbania powder, and mix well. Add 52g of 3.0wt% acetic acid solution to the above materials, knead into a plastic body, and then extrude into four-leaf clover strips with a diameter of 1.1mm on a front extrusion single screw extruder. Dry at 110℃ for 3h, and then roast at 600℃ for 3h to obtain an alumina carrier.

[0065] (2) Preparation of Catalyst

[0066] Weigh 100g of the above-mentioned alumina carrier, and use the saturation impregnation method to spray a solution prepared by 11g of ammonium molybdate (containing 82wt% of MoO3) and 8g of nickel nitrate (containing 25.2wt% of NiO) (wherein 8g of 18% ammonia water was added to the mixed solution during the preparation), after homogenization in the spraying equipment for 15min, drying at 110°C for 2h, and calcining at 480°C for 3h to obtain a catalyst, recorded as catalyst D1, which contains 8.0wt% of MoO3 and 1.8wt% of NiO.

[0067] Comparative Example 2

[0068] The catalyst prepared with reference to Example CN 101927169B is denoted as catalyst D2, and contains 8.0% MoO3 and 1.8% NiO.

[0069] Comparative Example 3

[0070] The catalyst prepared with reference to Example CN103998128A is denoted as catalyst D3, and contains 11.9% MoO3, 2.8% NiO, and 3.9% P2O5.

[0071] Comparative Example 4

[0072] The catalyst prepared with reference to Example CN105983413B is denoted as catalyst D4, and contains 5.0% WO3, 2.0% CoO, and 0.2% La2O3.

[0073] The physicochemical properties of the catalysts obtained in the above examples and comparative examples were tested, and the results are shown in Table 1.

[0074] Table 1 Physicochemical properties of catalysts obtained in the examples of the present invention and comparative examples

[0075] catalyst C1 C2 C3 C4 D1 D2 D3 D4 <![CDATA[Pore volume, cm 3 ·g -1 > 0.69 0.59 0.66 0.72 0.67 0.68 0.66 0.71 <![CDATA[Specific surface area, m 2 ·g -1 > 222 205 215 235 212 210 195 221 <![CDATA[MoO3,%]]> 8.0 11.9 10.3 / 8.0 8.0 11.9 / NiO, % 1.8 2.8 / / 1.8 1.8 2.8 / <![CDATA[WO3,%]]> / / / 5.0 / / / 5.0 CoO, % / / 3.1 2.0 / / / 2.0 <![CDATA[P2O5]]> / 3.9 / / / / 3.9 / Rare earth oxides, % / / / / / / / 0.2

[0076] Experimental example

[0077] This experimental example is used to illustrate the hydrogenation performance of the residue oil hydrogenation catalyst provided in the embodiment of the present invention, and to compare it with a comparative agent. The evaluation was carried out on a 300 mL small fixed bed hydrogenation device, and the above catalyst was evaluated by graded combination with a conventional demetallization catalyst in the art. The properties of the feed oil are shown in Table 2.

[0078] Table 2 Main properties of the test raw oil

[0079] <![CDATA[Density (20 °C), kg / m 3 > 968.2 (Ni+V), μg / g 80 sulfur,% 4.10 Nitrogen, μg / g 1800 Carbon residue,% 15.8

[0080] The evaluation conditions of this experimental example are shown in Table 3.

[0081] Table 3 Evaluation process conditions

[0082] Pressure, MPa 15 Hydrogen to oil ratio (volume) 1000 Reaction temperature, °C 385～395 <![CDATA[Liquid hourly space velocity, h －1 > 0.4

[0083] The activity after 8000 hours was used to compare the activity and stability of the catalysts, and the pore volume utilization of the catalysts was calculated by measuring the pore volume after the catalysts were extracted after 8000 hours of evaluation. The comparison results are shown in Table 4.

[0084] Table 4 Catalyst activity and pore volume utilization

[0085] catalyst Pore ​​volume utilization, % Desulfurization rate, % Denitrification rate, % Residual carbon removal rate, % C1 90 72 25 41 C2 89 80 31 48 C3 89 77 27 45 C4 91 70 23 40 D1 72 36 12 16 D2 74 38 14 18 D3 69 40 16 21 D4 75 39 15 20

[0086] As can be seen from Table 4, the catalyst operation time is 8000 hours, and the desulfurization rate, denitrification rate, and carbon residue removal rate of the catalysts C1, C2, C3, and C4 of the embodiments of the present invention are significantly higher than those of the comparative examples, and the catalyst pore volume utilization rates of the four embodiments of the present invention are all above 88%, which is much higher than the pore volume utilization rates of the four comparative example catalysts. This is because the active metals of the catalyst prepared by the present invention are reasonably distributed in the pores and have high activity utilization rates, while the pores of the comparative example catalysts are easily blocked during the reaction, resulting in the inability of the reaction raw materials to enter the remaining pores, and the active metals inside cannot play a role, resulting in a waste of resources. The catalyst prepared by the present invention shows high desulfurization, nitrogen and carbon residue activity, as well as superb activity stability, and extremely high utilization of active metals.

Claims

1. A method for preparing a residue oil hydrogenation catalyst, characterized in that: The steps include: (1) Pseudo-boehmite dry glue powder, sesbania powder and a glue solvent are mixed, kneaded and extruded into strips, dried and calcined at 300-380° C. to obtain an alumina carrier; (2) The alumina carrier is impregnated in an impregnation solution containing Group VIB and Group VIII metal compounds, dried, and then calcined again at 550-620° C. to obtain the finished residue oil hydrogenation catalyst.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the pseudo-boehmite dry glue powder to the sesbania powder is 100:(1-8).

3. The preparation method according to claim 1, characterized in that: The peptizing agent is acetic acid.

4. The preparation method according to claim 1, characterized in that: The impregnation liquid may also contain an acid or a base.

5. The preparation method according to claim 4, characterized in that: The acid is selected from phosphoric acid.

6. The preparation method according to claim 4, characterized in that: The base is selected from aqueous ammonia.

7. The preparation method according to claim 1, characterized in that: The calcination time in step (1) is 1-8 hours.

8. The preparation method according to claim 7, characterized in that: The calcination time in step (1) is 2-5 hours.

9. The preparation method according to claim 1, characterized in that: The re-roasting time in step (2) is 1-7h.

10. A residue oil hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 9, characterized in that: It includes an alumina carrier and an active metal oxide, wherein the active metal oxide includes Group VIB and Group VIII metal oxides; Based on the total weight of the catalyst, the content of the Group VIB metal oxide is 4-12%, and the content of the Group VIII metal oxide is 0.5-5%.

11. The residue hydrogenation catalyst according to claim 10, characterized in that The Group VIB metal is selected from tungsten and / or molybdenum.

12. The residue hydrogenation catalyst according to claim 10, characterized in that The Group VIII metal is selected from cobalt and / or nickel.

13. The residue hydrogenation catalyst according to claim 10, characterized in that The content of the Group VIII metal oxide is 0.9-4.5%.

14. The residue hydrogenation catalyst according to claim 10, characterized in that The pore volume of the catalyst is 0.3-2.0 mL / g.

15. The residue hydrogenation catalyst according to claim 14, characterized in that The pore volume of the catalyst is 0.40-1.5 mL / g.

16. The residue oil hydrogenation catalyst according to claim 10, characterized in that The specific surface area of ​​the catalyst is 70-300m 2 / g.

17. The residue hydrogenation catalyst according to claim 16, characterized in that The specific surface area of ​​the catalyst is 110-270m 2 / g.

18. Use of the residue oil hydrogenation catalyst prepared by the preparation method according to any one of claims 1 to 9 or the residue oil hydrogenation catalyst according to any one of claims 10 to 17 in residue oil hydrogenation.

19. The use according to claim 18, characterized in that The residual oil hydrogenation catalyst is used for the hydrodesulfurization and / or hydrodecarbonization of residual oil.

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