Preparation process of bimodal pore metalliferous residue oil demetallization agent carrier

Abstract

The application discloses a preparation process of a bimodal pore metal de-remover carrier for a residue oil, which comprises the following steps: (1) mixing an aluminum sulfate solution and a sodium metaaluminate solution, adjusting the pH of the system to be acidic, heating the system to react, and then aging the system after the reaction is completed; (2) continuously adding an alkaline substance to adjust the pH of the system to be alkaline, then heating the system to react, and then aging the system under the heating condition after the reaction is completed; (3) separating a solid product, washing the solid product, slurry treating the solid product, adding a liquid pore structure additive and a pH regulator into the system, and adjusting the pH of the system to be alkaline; (4) separating a solid product in the system in the step (3), and then performing a residual burning treatment on the solid product to obtain a modified material; mixing the modified material with pseudo-boehmite powder, a extrusion aid, a solid pore structure additive and silica sol, granulating and forming the mixture, and then sequentially performing drying and calcination treatment on the mixture to obtain the metal de-remover. The metal de-remover prepared by the process has the characteristics of bimodal pore and high strength.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of residual oil demetallization agent carrier, and particularly relates to a preparation process of a bimodal pore residual oil demetallization agent carrier. BACKGROUND

[0002] The following description in the background art is only directed to information which the present inventors believe to be relevant to the present application, and is intended to increase an understanding of the present application by providing some basic technical knowledge related to the present application, which does not necessarily have to constitute the knowledge commonly known by those skilled in the art.

[0003] Residual oil is the part with the highest boiling point in crude oil, which is rich in most of the sulfur, nitrogen, oxygen and other heteroatoms in crude oil, and contains inorganic salts or organic compounds of iron, calcium, nickel, vanadium and other metals. The nickel and vanadium metal impurities in residual oil mainly exist in colloid and asphaltene. This part of substances has large molecular weight and complex structure, and is difficult to diffuse, which causes the deactivation of residual oil hydrogenation demetallization agent. Therefore, the hydrogenation demetallization agent should have the bimodal pore characteristics of "diffusion pore" and "active pore". Among them, the macropore with a pore size of more than 100 nm, especially more than 500 nm, is suitable as a diffusion pore to provide a smooth channel for the diffusion and transmission of macromolecules, which is beneficial to the diffusion and reaction of impurities to the inside of the catalyst. And the mesopore with a pore size of 10-30 nm can provide more sufficient catalytic reaction surface and deposition site for the conversion of impurities. In addition, the demetallization agent should also have a larger pore volume and pore size. The pore volume is the basis for the capacity of the demetallization agent to accommodate impurities, and the demetallization agent should have a high capacity of impurities matching its high catalytic activity, and a larger pore size is beneficial to improve the accessibility of reactant macromolecules to the internal active center of the demetallization agent.

[0004] At present, the method for preparing the above-mentioned demetallization agent carrier is to add a large amount of macroporous organic and / or inorganic pore-expanding agent. However, the macroporous pore-expanding agent is relatively high in price, which leads to high cost of the carrier and weak market competitiveness of the product. At the same time, with the increasing obviousness of the heavy quality of crude oil, the processing load of the residual oil hydrogenation device is getting larger and larger, which puts forward higher requirements for the demetallization agent carrier--more macropore ratio (for example, >40% of >30 nm pore ratio), sufficient strength, larger pore volume. To increase the macropore ratio, the amount of pore-expanding agent needs to be increased, which on the one hand further increases the cost, and on the other hand, causes the bulk specific gravity of the demetallization agent carrier to decrease obviously and the strength to weaken. Therefore, the peptizing agent needs to be increased and the dry basis content needs to be improved, but this will cause the extrusion pressure to increase during manufacturing, and further cause the macropore retention to be low and the pore volume to decrease, which finally leads to the decrease of the capacity of the demetallization agent carrier to accommodate metal impurities. SUMMARY

[0005] The application provides a preparation process of a bimodal pore residue oil demetalizing agent carrier, and the demetalizing agent carrier prepared by the process has the characteristics of bimodal pore and high strength.

[0006] The application provides a preparation process of a bimodal pore residue oil demetalizing agent carrier.

[0007] (1) first step of neutralization: mixing an aluminum sulfate solution and a sodium aluminate solution in parallel, adjusting the pH of the system to 4-6 by adjusting the proportion of the two, and then reacting under heating.

[0008] (2) second step of neutralization: continuously adding an alkaline substance to the system in step (1), adjusting the pH of the system to alkaline, then reacting under heating, and aging under heating after completion.

[0009] (3) separating the product in the system in step (2), washing and filtering the product, then performing slurry treatment, simultaneously adding a liquid pore structure additive and a pH regulator, and adjusting the pH of the system to alkaline.

[0010] (4) separating the slurry in the system in step (3) to obtain a filter cake, and then performing pressing, and obtaining the modified material after the filter cake is burned to 20-30 wt%.

[0011] Further, in step (1), the heating temperature is 50-70 DEG C, and the reaction time is 10-20 min.

[0012] Further, in step (2), the pH of the system is adjusted to 7-9. Optionally, the alkaline substance includes any one of sodium carbonate, sodium bicarbonate, sodium hydroxide and the like.

[0013] Further, in step (2), the heating temperature is 60-90 DEG C, and the reaction time is 15-25 min. In this process, the pH of the system swings from acidic to alkaline, a large number of pseudoboehmite particles are generated, and the particles grow around the "seeds" formed in the first step.

[0014] Further, in step (2), the aging temperature is 70-95 DEG C, and the aging time is 120-240 min. The purpose of the aging is to make the pseudoboehmite particles obtained in step (2) continue to grow and stabilize the crystal structure.

[0015] Further, in step (3), the water washing time is 20-40 min, and the water washing temperature is 60-90℃.

[0016] Further, in step (3), the method of slurry treatment is as follows: the filter cake obtained by water washing is mixed with water at a mass ratio of 1:0.1-0.4, and then stirred for 20 min to form a flowable and uniform slurry.

[0017] Further, in step (3), the concentration of the liquid pore expander in the slurry is 50-150 g / L.

[0018] Further, in step (3), the liquid pore structure aid includes at least one of 4,4'-bis-sec-butylaminodiphenylmethane, 3-hydroxyethyloxyethyl-1-hydroxyethyl phenyl ether, 4-hydroxyethyloxyethyl-1-hydroxyethyl phenyl ether, polytetramethylene ether glycol bis-p-aminobenzoate, 4,4'-methylenebis(2-ethyl)aniline, 4,4'-methylenebis(2-methyl-6-ethylaniline), 3,3'-dimethyl-4,4-diaminodicyclohexylmethane, triallylisocyanurate, etc.

[0019] Further, in step (3), the pH adjuster includes any one of ammonia, ammonium bicarbonate, urea, monoethanolamine, triethanolamine, betaine, hexamethylenetetramine, etc.

[0020] Further, in step (4), the addition ratio of the solid pore structure aid is 5-10% and the addition ratio of the silica sol is 5-10% based on the weight of the finished product, and the remaining components are not limited and can be adjusted flexibly according to the product index requirements.

[0021] Further, the peptization index of the small-pore pseudo-boehmite powder is not less than 80%, and is preferably greater than 90%.

[0022] Further, in step (4), the solid pore structure aid includes at least one of solid 2,2'-dimethylolpropionic acid, solid 2,2'-dimethylolbutyric acid, solid hydroquinone dihydroxyethyl ether, solid resorcinol di(2-hydroxyethyl) ether, solid 4,4'-methylenebis(2,6-diethyl aniline), solid 4,4'-methylenebis(6-methyl-2-ethyl aniline), etc. In this step, the solid pore structure aid is used to increase the number of pores with a pore size of 30-100 nm and further increase the proportion of pores with a pore size of >30 nm, so as to help form more through pores, i.e., the connection channels of active pores and diffusion pores, to form a stepped pore channel structure.

[0023] Further, in step (4), the drying temperature is 110-130℃, and the drying time is 2-4 h.

[0024] Further, in step (4), the calcination temperature is 850-950 DEG C, and the calcination time is 2-4 h.

[0025] Further, in step (4), the slurry is separated, part of the liquid pore expander is taken out with the filter cake, and the other part enters the remaining liquid phase (filtrate), after supplementing the liquid pore expander and adjusting the concentration, the slurry treatment can be used again, so that the waste liquid is recycled, and the problem of high COD waste water is solved.

[0026] Compared with the prior art, the present application has at least the following beneficial technical effects:

[0027] Firstly, the present application adds a liquid pore structure additive at the specific time node of slurry treatment of the product in step (3), which fully acts with pseudo-boehmite particles, so that more large pores with a pore diameter > 100 nm are retained in the subsequent forming process. At the same time, the present application also adds a pH regulator at the slurry stage to fully exert the pore expansion effect, which also helps to retain more large pores with a pore diameter > 100 nm in the product. The subsequently added solid pore structure additive of the present application can directionally increase the proportion of pores with a pore diameter between 30-100 nm, thereby improving the compression resistance of the material in the forming process, making the large pore structure fully retained, and finally making the demetallizing agent carrier obtained by the present application not only have a bimodal pore characteristic, but also have a high strength characteristic. The present application directly adds a liquid pore structure additive at the slurry stage of the macroporous powder production process, so that the liquid pore structure additive can be more fully contacted with the pseudo-boehmite particles, preventing the collapse of the accumulated pores between the particles in the forming process, thereby playing a supporting role in the pore channel, and more > 100 nm pores can be retained in the forming process (more compression resistant).

[0028] Secondly, the pseudo-boehmite powder of the present application contains 5-15% of small pore powder with a pore volume of 0.4-0.6 mL / g and 15-30% of mesoporous powder with a pore volume of 0.8-0.1 mL / g. Through the above-mentioned collocation, the hydrogenation activity and the ability to accommodate impurities are regulated and controlled, and the obtained catalyst carrier bulk ratio is also improved, so that the hydrogenation and metal impurity accommodation capacity of the catalyst are more balanced. At the same time, the small pore powder has a high peptization index, so that it can be used as an adhesive, and the mesoporous powder is used as an auxiliary. This is because the effective pore proportion of the carrier prepared by the mesoporous powder is higher than that of the macroporous powder, and the mesoporous powder is more resistant to extrusion. The demetallization property of the macroporous powder is higher than that of the mesoporous powder. Therefore, the present application does not use organic or inorganic acid as a peptizing agent in the preparation of the demetallizing agent carrier, which helps to retain as many effective pores (active pores and diffusion pores) in the raw material as possible, and avoids the reduction of the pore expansion capacity of the pore expander due to the introduction of acid. BRIEF DESCRIPTION OF DRAWINGS

[0029] The accompanying drawings, which form a part of this specification, are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification. The embodiments of the application, together with its details, are described in this specification with the drawings and are shown in the figures, which are by way of illustration. As such, other embodiments of the application will occur to those skilled in the art upon consideration of this specification and may be learned from practice of the application. The purpose and scope of the application will be further appreciated based on the following detailed description, when read in conjunction with the figures, wherein:

[0030] Figure 1 The effect picture of the strip demetallization agent carrier prepared for the following example 1.

[0031] Figure 2 The mercury injection macropore detection result picture of the demetallization agent carrier prepared for the following example 2.

[0032] Figure 3 The mercury injection macropore detection result picture of the demetallization agent carrier prepared for the following comparative example 1. DETAILED DESCRIPTION

[0033] The application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the application and not to limit the scope of the application. The experimental methods in the following examples, if not otherwise specified, are usually carried out according to the conventional conditions or according to the conditions suggested by the manufacturers.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The materials and reagents used in the present application can be purchased through conventional routes. Unless otherwise specified, the materials and reagents used in the present application are used according to the conventional methods or according to the product instructions. In addition, any method and material similar or equivalent to those described can be applied in the present application. The preferred methods and materials described in the present application are only used for demonstration according to the description, drawings and specific embodiments.

[0035] Example 1

[0036] A preparation process of a bimodal pore residue oil demetallization agent carrier, comprising the following steps:

[0037] (1) First step of neutralization: mixing aluminum sulfate solution (Al2O3 content 4.6 g / 100 mL) and sodium aluminate solution (caustic ratio 1.25) in parallel, adjusting the pH of the system to 4.8 by adjusting the ratio of the two, and then reacting at 60°C for 20 min.

[0038] (2) Second step of neutralization: adding sodium carbonate solution (concentration 20 g / 100 mL) to the system of step (1), adjusting the pH of the system to 8.3, and then reacting at 70°C for 15 min, and aging at 85°C for 150 min after completion.

[0039] (3) Separating the product in step (2) system, squeezing, filtering, washing (washed with deionized water 3 times, 20 min each time, water washing temperature is 75℃), to remove the excess sodium ions and sulfate ions, to get the filter cake, filter cake burning residue 27.7%; The filter cake is treated with slurry, the mass ratio of filter cake to slurry water is 1:0.3, while adding liquid pore structure additive polytetramethylene ether glycol bis-p-aminobenzoic acid ester, and control the concentration of 100g / L; By adding an appropriate amount of pH adjuster triethanolamine, and adjust the pH of the system to 8.5, stirring for 20 min.

[0040] (4) Separating the slurry in step (3) system for squeezing, to get the filter cake, filter cake burning residue 26.9wt%, namely the modified filter cake. The above modified filter cake is dried at 120℃ for 2.5h, and then crushed to obtain the finished modified powder (burning residue 65.42%, 180 mesh standard sieve passing rate 99.4%).

[0041] The carrier dry base feeding is calculated as 1kg, that is, the modified filter cake 2600g, pseudo-boehmite powder small pore high viscosity powder USA (pore volume 0.60mL / g, burning residue 71.02%, peptization index 91.52%, self-produced by the company, same below) 140g, medium pore powder YH-25 (pore volume 0.98mL / g, burning residue 66.21%, self-produced by the company, same below) 302g, sesbania powder 60g, hydroxypropyl methyl cellulose 20g, citric acid monohydrate 30g and solid pore structure additive resorcinol di(2-hydroxyethyl) ether 75g are stirred in a kneader for 10 min, then a mixed solution of AN40 ammonia type silica sol 50g and make-up water 150g is added, and the kneading is continued for 20 min to form a shape; Φ1.80 cylindrical module is used for extrusion, the extrusion frequency is 18Hz, then 120℃ drying for 3h and 900℃ calcination for 4h are carried out in sequence, and the residual oil demetalizing agent carrier is obtained after completion.

[0042] Example 2

[0043] A preparation process of a bimodal pore residual oil demetalizing agent carrier, comprising the following steps:

[0044] (1) First neutralization: aluminum sulfate solution (Al2O3 content 4.7g / 100mL) and sodium aluminate solution (caustic ratio 1.28) are mixed in parallel, the pH of the system is adjusted to 5.1 by adjusting the ratio of the two, and then reacted at 55℃ for 15 min.

[0045] (2) Second neutralization: sodium carbonate solution (concentration 25g / 100mL) is continuously added to the system of step (1), the pH of the system is adjusted to 8.1, then reacted at 65℃ for 20 min, and aged at 90℃ for 180 min after completion.

[0046] (3) Separation of the product in step (2) system, it is squeezed, filtered, washed (washed with deionized water 3 times, 15 min each time, the washing temperature is 80℃), to remove the excess sodium ion and sulfate ion, to obtain the filter cake, filter cake burning residue 27.5%; The filter cake is treated with slurry, the mass ratio of filter cake to slurry water is 1:0.35, while adding liquid pore structure additive 3-hydroxyethyl oxyethyl-1-hydroxyethyl phenyl ether, and the concentration of 90g / L is added; By adding an appropriate amount of pH regulator betaine, and the pH of the system is adjusted to 8.4, stirring for 20 min.

[0047] (4) The slurry in step (3) is separated and squeezed to obtain a filter cake, and the filter cake has a burning residue of 26.4wt%. The modified filter cake is dried at 120℃ for 2h, and the finished modified powder is obtained after crushing (burning residue 65.23%, 180 mesh standard sieve passing rate 99.6%).

[0048] The carrier dry base feeding is calculated as 1kg, that is, the modified filter cake 2650g, pseudo-boehmite powder small pore high viscosity powder USA (pore volume 0.60mL / g, burning residue 71.02%, peptization index 91.52%) 140g, medium pore powder YH-25 (pore volume 0.98mL / g, burning residue 66.21%) 302g, sesbania powder 50g, hydroxypropyl methyl cellulose 20g, citric acid monohydrate 30g and solid pore structure additive 4,4'-methylenebis(6-methyl-2-ethylaniline) 75g are stirred in a kneader for 5min, then a mixed solution of AN40 ammonia type silica sol 60g and make-up water 130g is added, and the kneading is continued for 20min to form; Using Φ1.90 three-leaf module extrusion, the extrusion frequency is 15Hz, then 120℃ drying for 4h, 900℃ calcination for 3h, and the residue oil demetalizing agent carrier is obtained.

[0049] Example 3

[0050] A preparation process of a bimodal pore residue oil demetalizing agent carrier, comprising the following steps:

[0051] (1) First neutralization: aluminum sulfate solution (Al2O3 content 4.8g / 100mL) and sodium aluminate solution (caustic ratio 1.27) are mixed in parallel, the pH of the system is adjusted to 5.2 by adjusting the ratio of the two, and then reacted at 65℃ for 15min.

[0052] (2) Second neutralization: sodium carbonate solution (concentration 27g / 100mL) is continuously added to the system of step (1), the pH of the system is adjusted to 8.4, then reacted at 75℃ for 20min, and then aged at 85℃ for 180min.

[0053] (3) Separating the product in step (2) system, squeezing, filtering, washing (washed with deionized water 3 times, 15 min each time, washing temperature is 75℃), to remove the excess sodium ions and sulfate ions, to get the filter cake, filter cake burn residue 26.90%; the filter cake is treated with slurry, the mass ratio of filter cake to slurry water is 1:0.4, while adding liquid pore structure additive triallyl isocyanurate, and the concentration of 100g / L is controlled; by adding an appropriate amount of pH adjuster urea, and the pH of the system is adjusted to 8.2, stirring for 20 min.

[0054] (4) Separating the slurry in step (3) system for squeezing, to get the filter cake, filter cake burn residue 26.8wt%, namely the modified filter cake. The above modified filter cake is dried at 120℃ for 2h, and the finished modified powder is obtained after crushing (burn residue 66.12%, 180 mesh standard sieve passing rate 99.1%).

[0055] The carrier dry base feeding is calculated as 1kg, that is, the modified filter cake 2612g, pseudo-boehmite powder small pore high viscosity powder USA (pore volume 0.60mL / g, burn residue 71.02%, peptization index 91.52%) 214g, medium pore powder YH-25 (pore volume 0.98mL / g, burn residue 66.21%) 227g, sesbania powder 40g, hydroxypropyl methyl cellulose 20g, citric acid monohydrate 30g and solid pore structure additive hydroquinone dihydroxyethyl ether 80g are stirred in a kneader for 5min, then a mixed solution of AN40 ammonia type silica sol 60g and make-up water 160g is added, and the kneading is continued for 25min to form; Φ1.7×1.5 four-leaf clover module is used for extrusion, the extrusion frequency is 18Hz, then 120℃ drying for 4h and 900℃ calcination for 4h are carried out in turn, and the residual oil demetalizing agent carrier is obtained after completion.

[0056] Example 4

[0057] A preparation process of a bimodal pore residual oil demetalizing agent carrier, comprising the following steps:

[0058] (1) First neutralization: aluminum sulfate solution (Al2O3 content 4.9g / 100mL) and sodium aluminate solution (caustic ratio 1.26) are mixed in parallel, the pH of the system is adjusted to 5.1 by adjusting the ratio of the two, and then reacted at 60℃ for 20min.

[0059] (2) Second neutralization: sodium carbonate solution (concentration 29g / 100mL) is continuously added to the system of step (1), the pH of the system is adjusted to 8.5, then reacted at 70℃ for 15min, and aged at 80℃ for 210min after completion.

[0060] (3) Separating the product in step (2) system, squeezing, filtering, washing (washed with deionized water 3 times, 15 min each time, washing temperature is 75℃), to remove the excess sodium ions and sulfate ions, to get the filter cake, filter cake burning residue 26.70%; the filter cake was treated with slurry, the mass ratio of filter cake and slurry water was 1:0.4, while adding liquid pore structure additives 3-hydroxyethyl oxyethyl-1-hydroxyethyl phenyl ether, and the concentration of 150 g / L was controlled; by adding an appropriate amount of pH adjuster hexamethylenetetramine, and the system pH was adjusted to 8.1, stirring for 20 min.

[0061] (4) Separating the slurry in step (3) system for squeezing, to get the filter cake, filter cake burning residue 26.1wt%, namely the modified filter cake. The above modified filter cake was dried at 120℃ for 2h, and then crushed to obtain the finished modified powder (burning residue 66.12%, 180 mesh standard sieve passing rate 99.4%).

[0062] The carrier dry base feeding was calculated as 1 kg, that is, the modified filter cake 2682g, pseudo-boehmite powder small pore high viscosity powder USA (pore volume 0.60 mL / g, burning residue 71.02%, peptization index 91.52%) 214g, medium pore powder YH-25 (pore volume 0.98 mL / g, burning residue 66.21%) 227g, sesbania powder 50g, hydroxypropyl methyl cellulose 30g, citric acid monohydrate 20g and solid pore structure additive p-2,2'-dihydroxy methyl propionic acid 100g were stirred in a kneader for 5 min, then a mixed solution of AN40 ammonia type silica sol 80g and make-up water 100g was added, and the kneading was continued for 25 min to form; using Φ1.80 five-teeth module extrusion, extrusion frequency 18Hz, then sequentially drying at 120℃ for 2h, calcining at 900℃ for 2h, after completion, the residue oil demetalizing agent carrier was obtained.

[0063] Comparative Example 1

[0064] The comparative carrier preparation included the following steps:

[0065] (1) First neutralization: aluminum sulfate solution (Al2O3 content 4.8g / 100mL) and sodium aluminate solution (caustic ratio 1.25) were mixed in parallel, the pH of the system was adjusted to 5.1 by adjusting the ratio of the two, then reacted at 60℃ for 20 min.

[0066] (2) Second neutralization: sodium carbonate solution (concentration 25g / 100mL) was added to the system of step (1), the pH of the system was adjusted to 8.4, then reacted at 75℃ for 15 min, after completion, aging at 90℃ for 180 min.

[0067] (3) Separating the product in the system of step (2), squeezing, filtering, water washing (water washing 3 times with deionized water, each time 15 min, water washing temperature is 75°C) to remove excess sodium ions and sulfate ions, to obtain filter cake, filter cake burning residue is 26.70%; the filter cake is treated by slurry, the mass ratio of filter cake to slurry water is 1:0.4.

[0068] (4) Separating the slurry in the system of step (3) to obtain filter cake, filter cake burning residue is 25.5wt%, that is, the conventional filter cake. The above conventional filter cake is dried at 120°C for 2h, and after crushing, the finished conventional powder (burning residue 65.45%, 180 mesh standard sieve passing rate 98.9%) is obtained.

[0069] The carrier dry base feeding is calculated as 1kg, that is, the conventional powder 1069g, pseudo-boehmite powder small pore high viscosity powder USA (pore volume 0.60mL / g, burning residue 71.02%, peptization index 91.52%) 214g, medium pore powder YH-25 (pore volume 0.98mL / g, burning residue 66.21%) 227g, sesbania powder 50g, hydroxypropyl methyl cellulose 30g, citric acid monohydrate 20g and solid pore structure additive 2,2'-dimethylol propionic acid 100g are mixed in a kneader for 5min, then a mixed solution of liquid pore expander 3-hydroxyethyl oxyethyl-1-hydroxyethyl phenyl ether 175g, AN40 ammonia type silica sol 80g and supplementary water 1750g is added, and the mixing is continued for 25min to form; a Φ1.7×1.5 four-leaf clover module is used for extrusion, the extrusion frequency is 18Hz, then 120°C drying for 4h and 900°C calcination for 4h are carried out in sequence, and the residual oil demetalization agent carrier is obtained after completion.

[0070] Table 1 Performance index detection results of residual oil demetalization agent carriers prepared in each example and comparative example

[0071]

[0072] It can be seen that the above examples prepare the alumina strip carrier with high pore volume (0.85-0.90g / mL), bimodal pore distribution (>30nm pore ratio>40%), high strength and moderate price, compared with the comparative example (using pseudo-boehmite as raw material, adding liquid pore expander and solid pore expander during kneading), the >30nm pore ratio is only 27.12%, and the performance of the residual oil demetalization agent carrier is low.

[0073] The above only describes the preferred embodiments of the present application and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A preparation process for a bimodal porous residue oil demetallizing agent carrier, characterized in that, Includes the following steps: (1) First step of neutralization: aluminum sulfate solution and sodium aluminate solution are mixed in parallel flow, and the pH of the system is adjusted to between 4 and 6 by adjusting the ratio of the two. Then the reaction is carried out under heating conditions. (2) Second step of neutralization: Add alkaline substances to the system in step (1) to adjust the pH of the system to alkaline, then react under heating conditions, and then age under heating conditions after completion; (3) Separate the product from the system in step (2), wash it with water, filter it and then perform slurry treatment. At the same time, add liquid pore structure aid and pH adjuster, and adjust the pH of the system to alkaline. (4) Separate the slurry from the system in step (3) and press it to obtain a filter cake. The filter cake has a residue of 20-30 wt%, which is the modified material. Mix the modified material with boehmite powder, extrusion aid, solid pore structure aid, silica sol and supplementary water, knead and extrude it into shape, and then dry and calcine it in sequence. After completion, the residue oil demetallizing agent carrier is obtained. Among them, according to the weight of the finished product, the boehmite powder contains 5-15% of small pore powder with a pore volume of 0.4-0.6 mL / g and 15-30% of medium pore powder with a pore volume of 0.8-0.1 mL / g. In step (3), the concentration of the liquid pore-expanding agent in the slurry is 50-150 g / L; In step (3), the liquid pore structure aid includes at least one of the following: 4,4'-bis-sec-butylaminodiphenylmethane, 3-hydroxyethyloxyethyl-1-hydroxyethylphenyl diether, 4-hydroxyethyloxyethyl-1-hydroxyethylphenyl diether, polytetramethylene ether glycol bis-p-aminobenzoate, 4,4'-methylenebis(2-ethyl)aniline, 4,4'-methylenebis(2-methyl-6-ethylaniline), 3,3'-dimethyl-4,4-diaminodicyclohexylmethane, and triallyl isocyanate; Based on the weight of the finished product, the addition ratio of the solid pore structure additive in step (4) is 5-10%, and the addition ratio of the silica sol is 5-10%. In step (4), the solid pore structure aid includes at least one of the following: solid 2,2'-dimethylolpropionic acid, solid 2,2'-dimethylolbutyric acid, solid hydroquinone dihydroxyethyl ether, solid resorcinol di(2-hydroxyethyl) ether, solid 4,4'-methylenebis(2,6-diethylaniline), and solid 4,4'-methylenebis(6-methyl-2-ethylaniline).

2. The preparation process of the bimodal pore residue oil demetallizing agent carrier according to claim 1, characterized in that, In step (1), the heating temperature is 50~70℃ and the reaction time is 10~20min.

3. The preparation process of the bimodal pore residue oil demetallizing agent carrier according to claim 1, characterized in that, In step (2), the pH of the system is adjusted to between 7 and 9.

4. The preparation process of the bimodal pore residue oil demetallizing agent carrier according to claim 1, characterized in that, In step (2), the heating temperature is 60~90℃ and the reaction time is 15~25min; Alternatively, in step (2), the aging temperature is 70~95℃ and the aging time is 120~240min.

5. The preparation process of the bimodal pore residue oil demetallizing agent carrier according to claim 1, characterized in that, In step (3), the water washing time is 20~40 min and the water washing temperature is 60~90℃; Alternatively, in step (3), the slurry treatment method is as follows: the filter cake obtained by water washing is mixed with water at a mass ratio of 1:0.1-0.4 and stirred for 20 minutes to form a flowable and uniform slurry.

6. The preparation process of the bimodal pore residue oil demetallizing agent carrier according to any one of claims 1-5, characterized in that, In step (4), the drying temperature is 110~130℃ and the drying time is 2~4h; Alternatively, in step (4), the calcination temperature is 850~950℃ and the calcination time is 2~4h; Alternatively, in step (4), the remaining liquid phase after separating the slurry is used for the slurry treatment.

7. The preparation process of the bimodal pore residue oil demetallizing agent carrier as described in claim 3, characterized in that, The alkaline substance includes any one of sodium carbonate, sodium bicarbonate, and sodium hydroxide.

8. The preparation process of the bimodal pore residue oil demetallizing agent carrier as described in claim 1, characterized in that, In step (3), the pH adjuster includes any one of ammonia, ammonium bicarbonate, urea, monoethanolamine, triethanolamine, betaine, and hexamethylenetetramine.

9. The preparation process of the bimodal pore residue oil demetallizing agent carrier as described in claim 8, characterized in that, The colloidal index of the microporous pseudoboehmite powder is not less than 80%.

10. The preparation process of the bimodal pore residue oil demetallizing agent carrier as described in claim 9, characterized in that, The colloidal index of the microporous pseudoboehmite powder is greater than 90%.

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