A method for preparing a bimodal pore alumina penta dentate ball support

Abstract

The application discloses a preparation method of a bimodal pore alumina five-tooth ball carrier, which comprises the following steps: 1. raw materials pseudo-boehmite powder, extrusion aid, 5-15% hard template pore expander are dry-mixed for 5-15 min, 5-25% soft template pore expander aqueous solution is added, and stirring is continued for 20-60 min; then, water (50-70%) and acid (0-2%) are added, and kneading is performed until molding; 2. the extrusion frequency is 10-25 Hz, the module hole diameter is 3.0-7.0 mm, the cutter gap is 0.3-0.7 mm, and a circular arc-shaped or trapezoidal cutter is used; after the completion, the catalyst carrier is dried at 120 DEG C for 2-4 h, and then calcined at 850-950 DEG C for 2-4 h. Through the technical scheme, the alumina tooth ball carrier with a high bulk ratio (0.485-0.525 g / mL) and a bimodal pore distribution (the proportion of pores larger than 100 nm is not less than 15%) is prepared.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of preparation of residue hydroprocessing catalyst, in particular to a preparation method of bimodal pore alumina five-toothed spherical carrier. BACKGROUND

[0002] The following description in the background section only refers to the information which the present inventors believe to be relevant to the present application, and is not necessarily a complete description of the prior art. The description is intended to provide further appreciation of the application, and is not intended to mean that any or all prior art has been fully searched in order to identify aspects of the present application.

[0003] Residue is the highest boiling point part of 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. These impurities can easily cause equipment corrosion, catalyst poisoning and deactivation, poor product quality and other problems in the catalytic cracking process. Therefore, in order to meet the needs of producing clean fuel and improving economic benefits, the catalytic cracking unit has requirements or restrictions on the nickel and vanadium metal content of the residue feed.

[0004] The catalyst guard has more macroporous structure and higher bed voidage to remove and accommodate as many impurities as possible. The bed voidage gradually decreases along the catalyst bed downward, and reaches a similar voidage to the demetallization agent at the junction with the subsequent demetallization agent, so as to prevent the accumulation of raw materials at the junction of the guard and the demetallization agent due to the sharp decrease in voidage, causing serious local coking and increasing the bed pressure drop. On the one hand, as the catalyst with hydrogenation activity at the junction of the guard and the demetallization agent, it needs to further remove impurities and pre-remove part of the nickel and vanadium impurities, so it needs to have bimodal pore, larger pore volume and appropriate specific surface area, as well as bulk density and strength indicators. On the other hand, the traditional catalyst is in the form of a strip, which has the disadvantages of uneven packing, easy bridging, easy breaking during use, and further leading to channeling, bias flow and increase in bed pressure drop.

[0005] With the increasingly obvious crude oil heavy, the processing load of the residual oil hydrogenation device is getting larger and larger, so the performance of the catalyst is put forward higher requirements. However, the current catalyst carrier cannot meet the higher macropore ratio (mercury method, the macropore ratio of the pore diameter greater than 100 nm is greater than or equal to 15%) and the larger tap density (0.48-0.55 g / mL) at the same time. However, the present inventors found that if the tap density of the carrier is increased, the preparation raw material of the carrier will be dry, the extrusion pressure will increase sharply, and the macropore ratio of the pore diameter greater than 100 nm will be difficult to meet the above requirements. If the macroporous powder with high macropore ratio and strong metal impurity containing capacity is used to increase the macropore ratio, the hydrogenation activity of the catalyst will be insufficient, thereby affecting the hydrogenation catalytic activity. When the expansion agent is added to the preparation raw material to obtain a catalyst with a higher tap density, the anti-extrusion capacity is weak, and the macropore retention is less. Therefore, the current technology cannot simultaneously obtain the higher macropore ratio and the larger tap density of the catalyst carrier, which are mutually restricted performance indicators. SUMMARY

[0006] In view of the above problems, the present application provides a preparation method of a bimodal pore alumina five-tooth ball carrier, which effectively improves the macropore ratio and tap density of the catalyst carrier, and enables the catalyst to have more uniform hydrogenation and metal impurity containing capacity. In order to achieve the above application purpose, the present application discloses the following technical scheme.

[0007] A preparation method of a bimodal pore alumina five-tooth ball carrier, comprising the following steps:

[0008] (1) The raw materials pseudo-boehmite powder (mesopore powder with a pore volume of 0.8-1.0 mL / g and macropore powder with a pore volume of 1.0-1.2 mL / g), extrusion aid (consisting of sesbania powder, cellulose and citric acid monohydrate), 5-15% hard template pore expander are dry mixed for 5-15 min, 5-25% soft template pore expander aqueous solution (water 80-110%) is added, and stirring is continued for 20-60 min; then water (50-70%) and acid (0-2%) are added, and kneading is carried out until molding.

[0009] (2) The extrusion frequency is 10-25 Hz, the die hole diameter is 3.0-7.0 mm, the cutter gap is 0.3-0.7 mm, and the cutter is circular arc or trapezoidal. After completion, dry at 120℃ for 2-4h, then calcine at 850-950℃ for 2-4h, to obtain the catalyst carrier.

[0010] Further, the soft template pore expander can be added in solid form during dry mixing, or can be dissolved in water and added, preferably the latter.

[0011] Furthermore, the hard template pore-expanding agent can be one or a mixture of the following: micron-sized activated carbon powder, carbon black or hydrophilic modified carbon black, polymer (PP, PE, PET) micron powder, with preferred use of oil furnace carbon black, which is of moderate value.

[0012] Further, the soft template pore-expanding agent may be one or a mixture of the following: 4,4'-bis-sec-butylaminodiphenylmethane, 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutyric acid, hydroquinone dihydroxyethyl ether (solid), resorcinol di(2-hydroxyethyl) ether (solid), 3-hydroxyethyloxyethyl-1-hydroxyethylphenyl diether, 4-hydroxyethyloxyethyl-1-hydroxyethylphenyl diether, polytetramethylene ether diol bis-p-aminobenzoate, 4,4'-methylenebis(2-ethyl)aniline, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(6-methyl-2-ethylaniline), 4,4'-methylenebis(2-methyl-6-ethylaniline), 3,3'-dimethyl-4,4-diaminodicyclohexylmethane, and triallyl isocyanate.

[0013] Furthermore, the gel solubility index of the pseudoboehmite powder is >15%, preferably >20%.

[0014] Furthermore, the toothed ball can be a three-toothed ball or a five-toothed ball, and the tooth shape can be rectangular or angled, preferably angled (angle 30~45 degrees). o The toothed sphere can be made of toothed material; alternatively, a through hole can be added in the middle of the toothed sphere, and by matching different cutting blades, the tooth grooves can be connected to enhance the mass transfer effect. At the same time, the technology of this invention can also produce toothed cylindrical carriers.

[0015] Compared with the prior art, the present invention has at least the following beneficial technical effects: The boehmite powder of the present invention is composed of mesoporous powder with a pore volume of 0.8~1.0 mL / g and macroporous powder with a pore volume of 1.0~1.2 mL / g. Through the above combination, the hydrogenation activity and impurity-accommodating capacity are controlled, while also improving the bulk ratio of the obtained catalyst support, making the hydrogenation and metal impurity-accommodating capacity of the catalyst more balanced. Furthermore, the present invention uses a composite template pore expander formed by hard template pore expander and soft template pore expander, which improves the compressive strength of the raw material during the molding process. Through the above measures, the present invention simultaneously achieves the preparation of a toothed spherical catalyst support with rich macroporous structure and high bulk ratio, obtaining a bimodal porous alumina catalyst support, which can not only further remove impurities and scale, but also pre-remove some nickel and vanadium impurities by hydrogenation after loading active metals. Attached Figure Description

[0016] 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 more fully understood from the following detailed description taken in conjunction with the accompanying drawings.

[0017] Figure 1 The effect picture of the five toothed spherical bimodal pore alumina catalyst carrier prepared for the following example 1.

[0018] Figure 2 The mercury intrusion porosimetry macropore detection result picture of the catalyst carrier prepared for the following example 1.

[0019] Figure 3 The mercury intrusion porosimetry macropore detection result picture of the catalyst carrier prepared for the following comparative example 1. DETAILED DESCRIPTION

[0020] The application is further described in the following specific examples. It is to be understood that these examples are only used to illustrate the application and not intended 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.

[0021] 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 by conventional ways, and if not otherwise specified, the materials and reagents used in the present application are used according to the conventional ways in the art 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 present application is further described in the specification, drawings and specific embodiments, and the preferred implementation methods and materials described in the present application are only for demonstration.

[0022] Example 1

[0023] A preparation method of a bimodal pore alumina five toothed spherical carrier, comprising the following steps:

[0024] The carrier is measured according to 1 kg dry basis.

[0025] (1) kneading

[0026] Raw materials: pseudo-boehmite mesopore powder YH-25 (pore volume 0.98 mL / g, burn residue 66.21%, tight packing 0.4197 g / mL, peptization index 17.78%) 755 g and macropore powder YT-22 (pore volume 1.11 mL / g, burn residue 66.13%, tight packing 0.3578 g / mL, peptization index 23.13%) 1512 g, sesbania powder 50 g, hydroxypropyl methylcellulose 20 g, citric acid monohydrate 30 g and 100 g coconut shell activated carbon powder (325 mesh). The above raw materials are added into a kneader and dry mixed for 5 min. Then a water solution containing 100 g 4-hydroxyethyl oxyethyl-1-hydroxyethyl phenyl ether and 1100 g deionized water is added, and stirring is continued for 25 min; then a mixed solution of 600 g water and 5 g acetic acid is added, and kneading is carried out for 30 min to form a shape.

[0027] (2) Carrier shaping

[0028] A Φ6.0 five-toothed module (rectangular teeth) is used for extrusion, the extrusion frequency is 17.5 Hz, the cutter gap for pelletizing is 0.3 mm, and the cutter blade is arc-shaped (blade spacing 6.0 mm, depth 3.2 mm). After pelletizing is completed, drying is carried out at 120°C for 4 h, and then calcination is carried out at 930°C for 3 h, to obtain the alumina five-toothed ball catalyst carrier.

[0029] Example 2

[0030] A preparation method of a bimodal pore alumina five-toothed ball carrier, comprising the following steps:

[0031] The carrier is measured according to 1 kg of dry basis.

[0032] (1) Kneading

[0033] Raw materials: pseudo-boehmite mesopore powder YH-25 (pore volume 0.98 mL / g, burn residue 66.21%, tight packing 0.4197 g / mL, peptization index 17.78%) 755 g and macropore powder YT-22 (pore volume 1.11 mL / g, burn residue 66.13%, tight packing 0.3578 g / mL, peptization index 23.13%) 756 g, sesbania powder 60 g, hydroxypropyl methylcellulose 20 g, citric acid monohydrate 20 g and 75 g coconut shell activated carbon powder (325 mesh). The above raw materials are added into a kneader and dry mixed for 5 min. Then a water solution containing 150 g 4-hydroxyethyl oxyethyl-1-hydroxyethyl phenyl ether and 1050 g deionized water is added, and stirring is continued for 20 min; then a mixed solution of 550 g water and 10 g acetic acid is added, and kneading is carried out for 40 min to form a shape.

[0034] (2) Carrier shaping

[0035] The extrusion frequency is 15 Hz, the cutting clearance is 0.3 mm, and the circular blade (blade spacing 6.0 mm, depth 3.2 mm) is used. After the cutting is completed, drying is performed at 120°C for 4 h, and then calcination is performed at 930°C for 3 h, to obtain the alumina five-tooth ball catalyst carrier.

[0036] Example 3

[0037] A preparation method of a bimodal pore alumina five-tooth ball carrier, comprising the following steps:

[0038] The carrier raw material is measured according to 1 kg of dry basis.

[0039] (1) kneading

[0040] Raw materials: pseudo-boehmite mesopore powder YH-25 (pore volume 0.98 mL / g, burn residue 66.21%, tight stack 0.4197 g / mL, peptization index 17.78%) 755 g and macropore powder YT-22 (pore volume 1.11 mL / g, burn residue 66.13%, tight stack 0.3578 g / mL, peptization index 23.13%) 756 g, sesbania powder 60 g, hydroxypropyl methylcellulose 20 g, citric acid monohydrate 20 g and 50 g of coconut shell activated carbon powder (325 mesh). The above raw materials are added to the kneader and dry mixed for 5 min. Then, an aqueous solution containing 200 g of 4-hydroxyethyl oxyethyl-1-hydroxyethyl phenyl ether and 1000 g of deionized water is added, and stirring is continued for 20 min; then, a mixed solution of 550 g of water and 15 g of acetic acid is added, and kneading is performed for 40 min to form a shape.

[0041] (2) carrier shaping

[0042] The extrusion frequency is 15 Hz, the cutting clearance is 0.3 mm, and the circular blade (blade spacing 6.0 mm, depth 3.2 mm) is used. After the cutting is completed, drying is performed at 120°C for 4 h, and then calcination is performed at 930°C for 3 h, to obtain the alumina five-tooth ball catalyst carrier.

[0043] Example 4

[0044] A preparation method of a bimodal pore alumina five-tooth ball carrier, comprising the following steps:

[0045] The carrier raw material is measured according to 1 kg of dry basis.

[0046] (1) kneading

[0047] Raw materials: pseudo-boehmite mesopore powder YH-25 (pore volume 0.98 mL / g, burn residue 66.21%, tight packing 0.4197 g / mL, peptization index 17.78%) 755 g and macropore powder YT-22 (pore volume 1.11 mL / g, burn residue 66.13%, tight packing 0.3578 g / mL, peptization index 23.13%) 756 g, sesbania powder 60 g, hydroxypropyl methylcellulose 20 g, citric acid monohydrate 20 g and 50 g N660 carbon black. The above raw materials are added into a kneader and dry mixed for 10 min. Then, an aqueous solution containing 200 g 3,3'-dimethyl-4,4-diamino dicyclohexyl methane and 1000 g deionized water is added, and stirring is continued for 20 min; 530 g of water is further added, and kneading is carried out for 40 min to form a shape.

[0048] (2) Carrier shaping

[0049] Extrusion is carried out using a five-toothed module (rectangular teeth) with an outer circle diameter of Φ4.0, an extrusion frequency of 12.5 Hz, and a cutter gap of 0.3 mm for pelletizing. After pelletizing, drying is carried out at 120°C for 2 h, and then calcination is carried out at 930°C for 3 h to obtain the alumina five-toothed ball catalyst carrier.

[0050] Example 5

[0051] A preparation method of a bimodal pore alumina five-toothed ball carrier, comprising the following steps:

[0052] The carrier raw materials are measured according to 1 kg of dry basis.

[0053] (1) Kneading

[0054] Raw materials: pseudo-boehmite mesopore powder YH-25 (pore volume 0.98 mL / g, burn residue 66.21%, tight packing 0.4197 g / mL, peptization index 17.78%) 755 g and macropore powder YT-22 (pore volume 1.11 mL / g, burn residue 66.13%, tight packing 0.3578 g / mL, peptization index 23.13%) 756 g, sesbania powder 60 g, hydroxypropyl methylcellulose 20 g, citric acid monohydrate 30 g and 70 g PP micro powder (1000 mesh). The above raw materials are added into a kneader and dry mixed for 10 min, an aqueous solution containing 150 g 3,3'-dimethyl-4,4-diamino dicyclohexyl methane and 1050 g deionized water is added, and stirring is continued for 20 min; a mixed solution of 560 g water and 15 g acetic acid is further added, and kneading is carried out for 35 min to form a shape.

[0055] (2) Carrier shaping

[0056] Extrusion is carried out using a five-toothed module (tooth angle 30 oextrusion, extrusion frequency 12.5 Hz, granulation with a cutter gap of 0.3 mm, circular arc blade (blade spacing 6.0 mm, depth 3.2 mm). After granulation, drying at 120°C for 2 h, and then calcination at 930°C for 3 h, the alumina five-pronged ball catalyst carrier is obtained.

[0057] Comparative Example 1

[0058] A preparation method of a bimodal pore alumina five-pronged ball carrier, comprising the following steps:

[0059] The carrier feed is measured according to 1 kg of dry basis.

[0060] (1) kneading

[0061] Raw materials: pseudo-boehmite macroporous powder YT-22 (pore volume 1.11 mL / g, burn residue 66.13%, tight stack 0.3578 g / mL, peptization index 23.13%) 1512 g, sesbania powder 50 g, hydroxypropyl methyl cellulose 20 g, and 30 g of citric acid monohydrate. The above raw materials are added to the kneader and dry mixed for 5 min. A water solution containing 200 g of 4-hydroxyethyl oxyethyl-1-hydroxyethyl phenyl ether and 950 g of deionized water is added, and stirring is continued for 20 min; then a mixed solution of 550 g of water and 5 g of acetic acid is added, and kneading is carried out for 40 min to form a shape.

[0062] (2) carrier shaping

[0063] An outer circle diameter Φ6.0 five-pronged module (rectangular teeth) is used, the extrusion frequency is 15 Hz, the granulation is carried out with a cutter gap of 0.3 mm, and a circular arc blade (blade spacing 6.0 mm, depth 3.2 mm). After granulation, drying at 120°C for 2.5 h, and then calcination at 930°C for 3 h, the alumina five-pronged ball catalyst carrier is obtained.

[0064] Comparative Example 2

[0065] A preparation method of a bimodal pore alumina five-pronged ball carrier, comprising the following steps: the carrier feed is measured according to 1 kg of dry basis.

[0066] (1) kneading

[0067] Raw materials: pseudo-boehmite macroporous powder YT-22 (pore volume 1.11 mL / g, burn residue 66.13%, tight stack 0.3578 g / mL, peptization index 23.13%) 1512 g, sesbania powder 50 g, hydroxypropyl methyl cellulose 20 g, and 30 g of citric acid monohydrate. The above raw materials are added to the kneader and dry mixed for 5 min. A water solution containing 200 g of 4-hydroxyethyl oxyethyl-1-hydroxyethyl phenyl ether and 950 g of deionized water is added, and stirring is continued for 20 min; then a mixed solution of 550 g of water and 5 g of acetic acid is added, and kneading is carried out for 40 min to form a shape.

[0068] (2) Carrier shaping

[0069] A five-toothed module (rectangular tooth) with an outer circle diameter of Φ6.0 is adopted, the extrusion frequency is 15 Hz, the cutting knife gap is 0.3 mm, and the circular arc blade (blade spacing 6.0 mm, depth 3.2 mm) is used for cutting. After cutting, drying at 120℃ for 2.5h, and then calcining at 930℃ for 3h, the alumina five-toothed ball catalyst carrier is obtained.

[0070] The performance indicators of the alumina five-toothed ball catalyst carriers prepared in the above examples and comparative examples are detected, and the results are shown in Table 1.

[0071] Table 1: Measurement data of catalyst carrier samples prepared in the examples and comparative examples

[0072]

[0073] It can be seen that the technical scheme of each example has prepared an alumina toothed ball carrier with high bulk ratio (0.485-0.525g / mL) and bimodal pore distribution (the proportion of pores with a pore size of >100nm is not less than 15%). In comparison, the catalyst carrier prepared in the comparative example also has a high bulk ratio, but the proportion of bimodal pores with a pore size of >100nm is only 5.312%, which far fails to meet the requirements. This is because: the hard template pore expander and soft template pore expander are selected to improve the pressure resistance of the material forming process, realize the preparation of a toothed ball catalyst carrier with rich large pore structure and high bulk ratio; at the same time, in order to balance the hydrogenation and accommodate metal impurities, powders with different pore structures are selected, and the mesoporous powder also plays an auxiliary role in improving the bulk ratio; finally, by using pseudo-boehmite powder with a relatively high peptization index, more original large pore structures are retained under the premise of not adding an acidic peptizing agent, and the carrier strength meets the industrial application index.

[0074] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a bimodal pore alumina penta dentate support, characterized by, It comprises the following steps: (1) dry-mixing raw material pseudo-boehmite powder, extrusion aid, 5-15% hard template pore-expanding agent for 5-15 min, adding 5-25% aqueous solution of soft template pore-expanding agent, and continuing to stir for 20-60 min; then adding water and acid, and kneading to form; wherein: the pseudo-boehmite powder is composed of mesoporous powder with a pore volume of 0.8-1.0 mL / g and macroporous powder with a pore volume of 1.0-1.2 mL / g; the extrusion aid is composed of sesbania powder, cellulose and citric acid monohydrate; (2) extruding at a frequency of 10-25 Hz, with a die hole diameter of 3.0-7.0 mm, a cutter gap of 0.3-0.7 mm, and a circular arc or trapezoidal cutter; after completion, drying at 120℃ for 2-4 h, and then calcining at 850-950℃ for 2-4 h to obtain the carrier; the hard template pore-expanding agent is one or a mixture of several of the following: micron active carbon powder, carbon black or hydrophilic modified carbon black, PP micro powder, PE micro powder, PET micro powder; the soft template pore-expanding agent is one or a mixture of several of the following: 4,4'-bis-sec-butylaminodiphenyl methane, 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutyric acid, hydroquinone dihydroxyethyl ether, resorcinol di(2-hydroxyethyl) ether, 3-hydroxyethyloxyethyl-1-hydroxyethyl phenyl ether, 4-hydroxyethyloxyethyl-1-hydroxyethyl phenyl ether, polytetramethylene ether glycol bis-p-aminobenzoic acid ester, 4,4'-methylenebis(2-ethyl) aniline, 4,4'-methylenebis(2,6-diethyl aniline), 4,4'-methylenebis(6-methyl-2-ethyl aniline), 4,4'-methylenebis(2-methyl-6-ethyl aniline), 3,3'-dimethyl-4,4-diaminodicyclohexyl methane, triallylisocyanurate.

2. The method of making bimodal pore alumina penta dentate support of claim 1, wherein, The hard template pore-expanding agent is oil furnace carbon black.

3. The method for preparing the bimodal porous alumina five-toothed spherical carrier according to claim 1, characterized in that, The pseudo-boehmite powder has a peptization index of >15%.

4. The method of claim 3, wherein the method is characterized by, The pseudo-boehmite powder has a peptization index of >20%.

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