CN111889107B

CN111889107B - Hydrogenation protection catalyst and preparation method thereof

Info

Publication number: CN111889107B
Application number: CN201910371489.6A
Authority: CN
Inventors: 季洪海; 凌凤香; 王少军; 张会成; 沈智奇
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2019-05-06
Filing date: 2019-05-06
Publication date: 2022-07-08
Anticipated expiration: 2039-05-06
Also published as: CN111889107A

Abstract

The invention discloses a hydrogenation protection catalyst and a preparation method thereof. The catalyst comprises a carrier and a hydrogenation active component, wherein the carrier is volcanic rock particles with pore channels containing prismatic alumina, and the VIB group metal component and the VIII group metal component are respectively 2.0-8.5% and 0.5-3.5% by taking the total weight of the catalyst as a reference and taking oxides as a basis. The preparation method of the hydrogenation protection catalyst comprises the following steps: (1) soaking volcanic rock particles in an aluminum salt solution, and drying and roasting the soaked materials; (2) immersing the material obtained in the step (1) into an ammonium bicarbonate solution for sealing heat treatment, and then drying and roasting; (3) and (3) impregnating the material obtained in the step (2) with an impregnation liquid containing a hydrogenation active component, and drying and roasting the impregnated material to obtain the hydrogenation protection catalyst. The hydrogenation protection catalyst takes the modified volcanic rock rich in the prismatic structure as a carrier, has simple preparation process, cheap raw materials, strong impurity capacity and high demetalization activity, and is particularly suitable for a residual oil hydrotreating process.

Description

Hydrogenation protection catalyst and preparation method thereof

Technical Field

The invention relates to the field of preparation of catalytic materials, in particular to a hydrogenation protection catalyst and a preparation method thereof.

Background

Along with the aggravation of the trend of crude oil heaviness, the quality of raw materials used in various hydrogenation processes is poorer and poorer, the content of metal impurities and solid salt particles is high, the impurities are easy to deposit on the top of a hydrogenation reactor during hydrogenation reaction, so that materials are difficult to pass, the pressure drop of the hydrogenation reactor is increased, and the pressure drop is forced to be processed in a skimming mode.

The hydrogenation protective agent and the demetalization catalyst are one of the keys in the hydrogenation treatment technology. During the processing, metal impurities (such as V, Ni, Ca, Fe, etc.) and scales in the raw materials are easily deposited on the surface of the catalyst and in the gaps among catalyst particles, which can block the catalyst orifices to cause the deactivation of the catalyst on one hand, and cause the rapid rise of bed pressure drop to frequently stop the device and replace the catalyst on the other hand, thereby greatly reducing the service efficiency of industrial devices and the service life of the catalyst, and causing huge economic loss. Therefore, in order to ensure the long-term normal operation of the production device, before the main catalyst (such as hydrodesulfurization and hydrodenitrogenation catalysts), the hydrogenation protective agent and the demetallization catalyst must be filled. CN1966616A discloses a hydrogenation protective agent and a preparation method thereof, the protective agent contains an alumina carrier, an effective amount of hydrogenation active metal component and halogen loaded on the carrier, and the carrier is prepared by mixing one or more kinds of alumina and/or precursors of the alumina with at least one halogen-containing compound, molding and roasting. CN102649070A discloses a hydrogenation activity protective agent using alumina containing alkali metal as a carrier, a preparation method and an application thereof. The protective agent contains an alkali metal alumina carrier and a hydrogenation active component loaded on the carrier. The hydrogenation protective agent prepared by the prior art mainly takes alumina and/or modified alumina as a carrier, and the alumina carrier has higher cost in the production process, so that the price of the catalyst is higher, and how to select a proper alternative carrier becomes a research hotspot of people.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a hydrogenation protection catalyst and a preparation method thereof. The hydrogenation protection catalyst takes the modified volcanic rock rich in the prismatic structure as a carrier, the preparation process is simple, the raw materials are cheap, and the prepared hydrogenation protection agent has the characteristics of strong impurity capacity, high demetalization activity and the like, and is particularly suitable for the residual oil hydrogenation treatment process.

The hydrogenation protection catalyst comprises a carrier and a hydrogenation active component loaded on the carrier, wherein the carrier is volcanic rock particles with pore channels containing prismatic alumina, and the weight of the volcanic rock particles is taken as a reference, the volcanic rock particles are 50-90 wt%, the prismatic alumina particles are 10-50 wt%, and the preferred weight is 15-45%; the prismatic alumina is alternately filled in the pore channels; the hydrogenation active component is selected from at least one VIB group metal component and at least one VIII group metal component, and the VIB group metal component is 2.0-8.5%, preferably 3.5-7.5% and the VIII group metal component is 0.5-3.5%, preferably 1.5-3% on the basis of the total weight of the catalyst and calculated by oxides. The VIB group metal component is W and/or Mo. The VIII family metal component is Co and/or Ni.

In the hydrogenation protection catalyst, the prismatic alumina is a diagonal prismatic and/or a right prismatic alumina; the prismatic alumina can be in other polygonal column shapes such as quadrangular column shape, pentagonal column shape, hexagonal column shape and the like; the length of the ridge is about 1-15 μm, preferably 3-10 μm, and the side length of the bottom surface is about 100-500nm, preferably 150-300 nm.

The specific surface area of the hydrogenation protection catalyst is 40-120m²The pore volume is 0.3-0.7mL/g, the pore volume occupied by the pores with the pore diameter of more than 1 μm is 10-30% of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-1000nm is 20-50% of the total pore volume, and the crushing strength is 100-300N/particle.

In the hydrogenation protection catalyst, the particle size of the carrier particles is 1-10mm, preferably 3-5 mm.

The preparation method of the hydrogenation protection catalyst comprises the following steps:

(1) soaking volcanic rock particles in an aluminum salt solution, and drying and roasting the soaked materials;

(2) immersing the roasted material in the step (1) into an ammonium bicarbonate solution for sealing heat treatment, and drying and roasting the heat-treated material to obtain volcanic rock particles with prismatic alumina in pore channels;

(3) and (3) impregnating the material obtained in the step (2) with an impregnation liquid containing a hydrogenation active component, and drying and roasting the impregnated material to obtain the hydrogenation protection catalyst.

In the method, the volcanic rock particles in the step (1) are volcanic rocks with micron-sized pore canals in the inner pore canals, the diameter of the micron-sized pore canals is preferably 1-50 microns, and the particle size of the volcanic rocks is preferably 1-10mm and preferably 3-5 mm. The volcanic rock particles are commercially available products, and the particle size can be screened according to needs.

In the method, the aluminum salt solution in the step (1) is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate aqueous solutions, and also can be an ethanol solution of aluminum isopropoxide, preferably an aluminum nitrate aqueous solution, the mass percent concentration of the aluminum salt solution is 25-45%, one-time impregnation or multiple-time impregnation can be adopted during impregnation, preferably multiple-time impregnation is adopted, the impregnation times are preferably 2-4 times, drying and roasting treatment are carried out after each impregnation when multiple-time impregnation is adopted, the drying temperature is 160-.

In the method, the mass ratio of the amount of the ammonium bicarbonate aqueous solution in the step (2) to the material obtained in the step (1) is 4:1-8:1, and the mass percentage concentration of the ammonium bicarbonate aqueous solution is 15-25%.

In the method of the invention, the sealing heat treatment temperature in the step (2) is 120-.

In the method of the invention, the drying temperature in the step (2) is 160 ℃ and the drying time is 2-10 hours, the roasting temperature is 900 ℃ and the roasting time is 4-10 hours.

In the method of the present invention, the dipping solution containing hydrogenation active metals in step (3) is a solution containing group VIB and/or group VIII metals, and may be an acid solution, an alkali solution or an aqueous solution. The group VIB metal is selected from W and/or Mo, and the group VIII metal is selected from Co and/or Ni. The content of VIB group metal oxide in the solution is 2.0-10g/100mL, and the content of VIII group metal oxide is 0.5-3g/100 mL.

In the method of the present invention, the impregnation in step (3) may be performed by spray impregnation, saturated impregnation or supersaturated impregnation. The drying condition is that the drying is carried out for 1 to 5 hours at the temperature of 100-130 ℃; the roasting condition is roasting at 400-550 ℃ for 2-10 hours.

Compared with the prior art, the invention has the following advantages:

(1) the hydrogenation protective agent takes volcanic rock particles containing prismatic alumina as a carrier, and the preparation method is

The method is simple, the raw materials are cheap and easy to obtain, and the production cost and the production period of the catalyst are greatly reduced;

(2) volcanic rock particles containing prismatic alumina, and the micron-sized volcanic rock particles are fully utilized

And prismatic alumina grows in the micron-sized pore channels, and the prismatic alumina is mutually staggered to form a net structure, so that the volcanic rock carrier has the micron-sized pore channels and simultaneously has higher content of the 100-1000nm pore channels, and the hydrogenation protective agent prepared by taking the volcanic rock as the carrier has strong impurity capacity and high demetallization activity.

Drawings

FIG. 1 is a SEM image of a cross section of a volcanic rock raw material particle.

FIG. 2 is a SEM image of a cross-section of a volcanic rock particle containing prismatic alumina prepared in example 1.

Fig. 3 is an SEM image of prismatic alumina in volcanic rock particles prepared in example 1.

Detailed Description

The technical solutions and effects of the present invention are further described below with reference to the following examples, but the present invention is not limited to the following examples.

Application N₂Physical adsorption-desorption methods were used to characterize the pore structures of the examples and comparative examples, and the specific operations were as follows: adopting ASAP-2420 type N₂And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. And (3) carrying out vacuum treatment on a small amount of sample at 300 ℃ for 3-4 hours, and finally placing the product under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the pore size distribution and the pore volume are obtained according to a BJH model.

The scanning electron microscope is used for representing the microstructure of a sample, and the specific operation is as follows: and characterizing the microstructure of the sample by adopting a JSM-7500F scanning electron microscope, wherein the accelerating voltage is 5KV, the accelerating current is 20 muA, and the working distance is 8 mm.

Mercury pressing method: the pore diameter distribution of the samples of the examples and the comparative examples is characterized by applying a mercury porosimeter, and the specific operation is as follows: and characterizing the distribution of sample holes by adopting a full-automatic mercury porosimeter model U.S. Mac AutoPore 9500. The samples were dried, weighed into an dilatometer, degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and filled with mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm^-1The distribution ratio of pore diameter of 100nm or more is measured by mercury intrusion method.

The volcanic rock particles are purchased from Zhongxing stone factories in Town City, the particle diameter is 3-5mm, the specific surface area is 3m²The pore volume is 0.06mL/g, the pores larger than 1 mu m account for 70% of the total pore volume, and the pores of 100-1000nm account for 5% of the total pore volume.

Example 1

Weighing 50 g of volcanic rock, placing the volcanic rock in a beaker, adding 500mL of 32 mass percent aluminum nitrate solution into the beaker, soaking for 1 hour to ensure that the volcanic rock is adsorbed and saturated, drying the soaked material at 120 ℃ for 6 hours, and roasting at 750 ℃ for 6 hours. The roasted material is dipped and treated for 2 times by the same method.

Weighing 20 g of the treated volcanic rock, placing the 20 g of the treated volcanic rock into 110 g of ammonium bicarbonate aqueous solution with the mass concentration of 19%, transferring the mixed material into an autoclave, sealing, heating at 145 ℃ for 5.5 hours, drying the carrier at 110 ℃ for 6 hours, and roasting at 800 ℃ for 4 hours to obtain the volcanic rock H1 containing prismatic alumina, wherein a scanning electron microscope photo is shown in figure 1.

Weighing 20 g of volcanic rock containing prismatic alumina, and adding 50mL of Mo-Ni-NH₃Solution (according to MoO content in the final catalyst)₃5.5wt% and NiO1.6 wt%) for 2 hours, filtering out the excess solution, drying at 120 ℃ for 5 hours, and then roasting at 550 ℃ for 5 hours to obtain the hydrogenation protective agent Cat-1, wherein the properties of the catalyst are shown in Table 1.

Example 2

In the same manner as in example 1 except that the mass concentration of aluminum nitrate was 36%, the amount of the ammonium hydrogencarbonate solution used in the heat treatment was 130 g, and the mass concentration of the solution was 22%. The heat treatment temperature was 130 ℃ and the treatment time was 6 hours. The hydrogenation protective agent Cat-2 is prepared, and the properties of the catalyst are shown in the table 1.

Example 3

In the same manner as in example 1 except that the mass concentration of aluminum nitrate was 40%, the number of times of aluminum salt impregnation was 2, the amount of the ammonium hydrogencarbonate solution used in the heat treatment was 150 g, and the mass concentration of the solution was 17%. The heat treatment temperature was 120 ℃ and the treatment time was 7 hours. The hydrogenation protective agent Cat-3 is prepared, and the properties of the catalyst are shown in the table 1.

Example 4

In the same manner as in example 1 except that the mass concentration of aluminum nitrate was 25%, the amount of the ammonium hydrogencarbonate solution used in the heat treatment was 95 g, and the mass concentration of the solution was 24.5%. The heat treatment temperature was 150 ℃ and the treatment time was 4.5 hours. Modified macroporous material A4 was obtained, the material properties are shown in Table 1. The hydrogenation protective agent Cat-4 is prepared, and the properties of the catalyst are shown in the table 1.

Comparative example 1

The same as example 1, except that all the supports of the hydrogenation protective agent are conventional alumina supports, the alumina supports are prepared according to the method of patent CN1488441A example 1, and the comparative hydrogenation protective agent Cat-5 is prepared, and the properties of the catalyst are shown in Table 1.

Comparative example 2

Similar to example 1, except that no heat treatment was performed after the volcanic rock was impregnated with aluminum salt, no prismatic alumina was generated in the micron-sized channels of volcanic rock, and comparative hydrogenation protecting agent Cat-6 was obtained, and the catalyst properties are shown in Table 1.

Comparative example 3

Similar to example 1, except that no aluminum salt was impregnated into the volcanic rock, no prismatic alumina was formed in the micron-sized channels of the volcanic rock, and comparative hydrogenation protectant Cat-7 was prepared, and the catalyst properties are shown in Table 1.

Comparative example 4

The same as example 1, except that volcanic rock is directly used as a carrier to prepare the comparative hydrogenation protective agent Cat-8, and the properties of the catalyst are shown in Table 1.

TABLE 1 Hydroprotectant Properties

Example 5

The following example illustrates the catalytic performance of the hydroprotectant Cat-1-Cat-8.

The hydrogenation protection catalyst Cat-1-Cat-4 of the invention and the comparative hydrogenation protection catalyst Cat-5-Cat-8 are respectively filled in a fixed bed hydrogenation reactor, the treated raw materials (see Table 2) have the following test conditions: the reaction temperature is 385 ℃, the volume ratio of hydrogen to oil is 1000, and the liquid hourly space velocity is 1.0h^-1The hydrogen partial pressure was 14MPa, the operation was continued for 2000 hours, and the impurity removal properties are shown in Table 3.

TABLE 2

TABLE 3 evaluation results of catalysts

From the results in table 3, it can be seen that the hydrogenation protective agent prepared by using volcanic rock containing prismatic alumina as a carrier has comparable nickel and vanadium removal rates and slightly higher calcium and iron removal rates compared with the hydrogenation protective agent using conventional alumina as a carrier. Compared with the hydrogenation protective agent prepared by using volcanic rock without prismatic alumina as a carrier, the hydrogenation protective agent has higher Ca, Fe, Ni and V removal rate and good stability.

Claims

1. The hydrogenation protection catalyst is characterized by comprising a carrier and a hydrogenation active component loaded on the carrier, wherein the carrier is volcanic rock particles with pore channels containing prismatic alumina, and the weight of the volcanic rock particles is 50-90 wt% and the weight of the prismatic alumina particles is 10-50 wt% based on the weight of the carrier; the prismatic alumina is alternately filled in the pore channels; the hydrogenation active component is selected from at least one VIB group metal component and at least one VIII group metal component, and the VIB group metal component accounts for 2.0-8.5% and the VIII group metal component accounts for 0.5-3.5% of the total weight of the catalyst and calculated by oxides.

2. The catalyst of claim 1, wherein: the VIB group metal component is W and/or Mo; the VIII family metal component is Co and/or Ni.

3. The catalyst of claim 1, wherein: the prismatic alumina is a beveled prismatic and/or a straight prismatic alumina; the prismatic alumina is quadrangular, pentagonal or hexagonal; the length of the edge is 1-15 μm, and the side length of the bottom surface is 100-500 nm.

4. The catalyst of claim 3, wherein: the length of the edge is 3 to 10 μm, and the side length of the bottom surface is 150 to 300 nm.

5. The catalyst of claim 1, wherein: the specific surface area is 40-120m²The pore volume is 0.3-0.7mL/g, the pore volume occupied by the pores with the pore diameter of more than 1 μm is 10-30% of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-1000nm is 20-50% of the total pore volume, and the crushing strength is 100-300N/particle.

6. The catalyst of claim 1, wherein: the particle size of the carrier particles is 1-10 mm.

7. The catalyst of claim 6, wherein: the particle size of the carrier particles is 3-5 mm.

8. A method for preparing a hydrogenation protection catalyst according to any one of claims 1 to 7, characterized by comprising: (1) soaking volcanic rock particles in an aluminum salt solution, and drying and roasting the soaked materials; (2) immersing the material obtained in the step (1) into an ammonium bicarbonate solution for sealing heat treatment, and drying and roasting the heat-treated material to obtain volcanic rock particles with prismatic alumina in pore channels; (3) and (3) impregnating the material obtained in the step (2) with an impregnation liquid containing a hydrogenation active component, and drying and roasting the impregnated material to obtain the hydrogenation protection catalyst.

9. The method of claim 8, wherein: the volcanic rock particles in the step (1) are volcanic rocks with micron-sized inner pore canals, and the particle size of the volcanic rocks is 1-10 mm.

10. The method of claim 8, wherein: the aluminum salt solution in the step (1) is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate aqueous solution or aluminum isopropoxide ethanol solution, and the mass percent concentration of the aluminum salt solution is 25-45%.

11. The method of claim 8, wherein: the impregnation in the step (1) adopts one-time impregnation or multiple times of impregnation; when multiple times of impregnation are adopted, drying and roasting treatment are carried out after each impregnation; the drying temperature is 100-160 ℃, the drying time is 2-10 hours, the roasting temperature is 600-900 ℃, and the roasting time is 4-10 hours.

12. The method of claim 8, wherein: the mass ratio of the amount of the ammonium bicarbonate aqueous solution in the step (2) to the material obtained in the step (1) is 4:1-8:1, and the mass percentage concentration of the ammonium bicarbonate aqueous solution is 15% -25%.

13. The method of claim 8, wherein: the sealing heat treatment temperature in the step (2) is 120-160 ℃, and the constant temperature treatment time is 4-8 hours.

14. The method of claim 8, wherein: the drying temperature in the step (2) is 160 ℃ and the drying time is 2-10 hours, the roasting temperature is 900 ℃ and the roasting time is 4-10 hours.

15. The method of claim 8, wherein: the dipping solution containing the hydrogenation active component in the step (3) is a solution containing VIB group and/or VIII group metals, the content of VIB group metal oxides in the solution is 2.0-10g/100mL, and the content of VIII group metal oxides in the solution is 0.5-3g/100 mL.

16. Use of the hydrogenation protection catalyst according to any one of claims 1 to 7 in heavy oil hydroprocessing.