Background
Since the 21 st century, petroleum shortage and the world oil refining enterprises are increasingly heavy in processing crude oil, and the contents of sulfur, nitrogen and heavy metals are obviously increased. With the increasing strictness of environmental regulations, oil refining enterprises need to adopt clean production processes for clean fuel production. Meanwhile, the demand of the oil market for high-quality middle distillate oil (such as jet fuel and diesel oil products) is increasing. To date, the world oil demand continues to develop towards reducing heavy oil and fuel oil and increasing high-quality middle distillate oil (aviation kerosene and diesel oil).
The amorphous silica-alumina is widely used as an acidic carrier material in a hydrocracking catalyst, and has the advantages of large pore diameter, low acid center density, good nitrogen resistance, good product quality and the like. As a carrier of the supported catalyst, the amorphous silica-alumina needs to have high specific surface area and large pore volume, so that the metal supported dispersity and coking resistance and carbon deposition resistance are improved, the catalyst reaction performance is improved, and the service life of the catalyst is prolonged. The cracking activity of the amorphous silica-alumina is much lower than that of the molecular sieve, the amorphous silica-alumina and the molecular sieve have obvious differences in acid center number, acid strength, acid distribution and the like and pore channel structures, and the amorphous silica-alumina and the molecular sieve have higher cracking reaction selectivity to macromolecules existing in the petroleum refining feeding process, particularly macromolecules which cannot enter the pore channels of the molecular sieve, so that the amorphous silica-alumina and the molecular sieve have larger differences in performance.
Amorphous aluminosilicates have a low density and a high strength, and contain not only B acids, which provide cracking activity, but also a certain amount of L acids, and are less prone to excessive cracking. Amorphous silica alumina has more excellent mesoporous distribution properties than alumina and molecular sieves. By changing the preparation conditions, the specific surface area and the pore volume of the amorphous silica-alumina can be adjusted in a wider range, and the acid distribution and the pore distribution of the silica-alumina carrier can be modulated.
CN103785481a discloses a carbonization method for preparing high silicon macroporous amorphous silica alumina dry gel. The method is characterized in that carbon dioxide gas is introduced to perform neutralization reaction and aging process under high pressure and low temperature to obtain amorphous silicon aluminum, and the preparation process is performed in a specific environment, so that the method is not beneficial to industrial scale-up production. CN102039197a discloses a modification method for preparing amorphous silica-alumina by a carbon dioxide neutralization method, so as to promote the pore structure of amorphous silica-alumina and improve acid distribution, avoid excessive cracking of raw materials, and facilitate improvement of product selectivity. CN101491774B discloses a method for preparing high silicon amorphous silica-alumina. The method is used for simultaneously precipitating the silicon oxide and the aluminum oxide, and modifying the silicon oxide by using the organic silicon to obtain a high-silicon product, wherein the organic silicon is required to be roasted in the process, and the energy consumption in the preparation process is high.
In recent years, with the rapid development of petrochemical industry, as amorphous silica-alumina has outstanding performance in selectively cracking polycyclic aromatic hydrocarbon, the demand of the market for amorphous silica-alumina is continuously increasing, but environmental protection indexes are continuously increasing, and the clean production of industrial catalysts and related raw materials is receiving more and more attention. The existing amorphous silica alumina dry gel product produced by the aluminum chloride or aluminum sulfate method can discharge a large amount of ammonia nitrogen waste, the problem is increasingly serious, and the cleaning product of the amorphous silica alumina dry gel product becomes more and more important. Meanwhile, the silicon-aluminum ratio, the pore volume, the specific surface area and the like of the amorphous silicon-aluminum are improved, and the method has positive significance for improving the catalytic performance of the amorphous silicon-aluminum.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of amorphous silicon aluminum, and the amorphous silicon aluminum prepared by the method has the characteristics of high specific surface area and large pore volume, is easy for mass production, and can be used as an acidic component in a hydrocracking catalyst.
The first aspect of the invention provides a method for preparing amorphous silica-alumina, comprising the following steps:
(1) Preparing an aluminum source solution, adding an inorganic acid solution, adjusting the pH value, and controlling the temperature to be 15-45 ℃ to obtain a material I;
(2) Preparing a silicon source solution, and adding the silicon source solution into the material I obtained in the step (1) in a stirring state to obtain a material II;
(3) Preparing a mixed alkali solution of sodium hydroxide and sodium bicarbonate;
(4) And (3) adding the mixed alkali solution obtained in the step (3) and the material II into a reactor in parallel flow, and aging to obtain amorphous silicon-aluminum.
Further, in the step (1), the concentration of the aluminum source solution is 3 to 25g of Al 2 O 3 Per 100mL, preferably 8-15 g Al 2 O 3 100mL. The aluminum source is one or more of sodium metaaluminate, aluminum sulfate and the like. The concentration of the inorganic acid solution is 15-30 g/100mL. The inorganic acid is one or more of nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid and the like.
Further, in the step (1), the pH is 0 to 4, preferably 1 to 3. After the addition of the mineral acid, the temperature is preferably controlled to 20 to 35 ℃.
Further, in the step (2), the concentration of the silicon source solution is 5 to 25g of SiO 2 100mL, preferably 8-15 g SiO 2 100mL. The silicon source is one or more of sodium silicate, silica sol, white carbon black and the like.
Further, the volume ratio of the silicon source solution in the step (2) to the aluminum source solution in the step (1) is 1:0.5-1:5, preferably 1:1-1:3.
Further, in the step (3), the mass ratio of sodium hydroxide to sodium bicarbonate in the mixed alkali solution is 8:1-1:1, preferably 4:1-4:3.
Further, in the step (4), the mixed alkali solution and the material II are in parallel flow, and the pH is controlled to be 6.5-8.5, preferably 7.0-8.0 by controlling the addition amount of the mixed alkali solution.
Further, in the step (4), the aging temperature is 30 to 80 ℃, preferably 40 to 70 ℃, and the aging time is 0.5 to 6 hours, preferably 1 to 3 hours.
Further, in the step (4), after aging, amorphous silica-alumina is obtained through the steps of post treatment, such as filtration, drying and the like. The drying conditions are as follows: drying at 90-130 deg.c for 5-25 hr.
In a second aspect the present invention provides an amorphous silica-alumina prepared according to the above process, said amorphous silica-alumina beingThe properties of the shaped silica-alumina are as follows: specific surface area of 280-500 m 2 Per gram, pore volume of 0.60-1.10 cm 3 /g,SiO 2 The mass content is 20% -70%, preferably 40% -65%.
In a third aspect the invention provides the use of said amorphous silica alumina.
The application is that amorphous silica alumina is used in a hydrocracking catalyst, and the hydrocracking catalyst is suitable for a hydrocracking process of condensed ring macromolecules.
Compared with the prior art, the invention has the following advantages:
the process for preparing the amorphous silicon aluminum by the method has the advantages of simple path, low cost and controllable path, and the raw materials do not contain ammonia nitrogen compounds, so that clean production can be realized. The obtained amorphous silica-alumina product has stable property and higher SiO content 2 The content of the catalyst completely meets the performance requirement of the hydrocracking catalyst, can be used as a carrier component of the hydrocracking catalyst, and is applied to the petroleum refining process.
Detailed Description
The following examples further illustrate the preparation of the present invention, but are not intended to limit the invention.
In the invention, sample XRD is measured by an X-ray diffractometer of D/Max-2500 of RIGAKU company of Japan; n (N) 2 Adsorption-desorption characterization was determined using ASAP 2420 from MICROMERITICS Inc. of America.
Example 1
Preparing Al with concentration of 10g 2 O 3 100mL of aluminum sulfate solution, adding sulfuric acid solution L with the concentration of 20g/100mL, controlling the pH value to be 1 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 25 ℃; preparation of 10g SiO 2 100mL of water glass solution, slowly adding water glass drops into the material I in a stirring state for 60min, wherein the volume ratio of the aluminum sulfate solution to the water glass solution is 1:1, and obtainingA material II; sodium hydroxide and sodium bicarbonate are added according to the mass ratio of 2:1 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH value of the system to be 7.0, aging for 2 hours at 60 ℃, filtering, and drying for 24 hours at 100 ℃ to obtain the product. The XRD pattern of this product is shown in FIG. 1.
Example 2
Preparing Al with concentration of 5g 2 O 3 100mL of aluminum sulfate solution, adding 25g/100mL of sulfuric acid solution L, controlling pH=2 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 30 ℃; preparation of 8g SiO 2 100mL of water glass solution, slowly dropwise adding the water glass into the material I in a stirring state within 60min, wherein the volume ratio of the aluminum sulfate solution to the water glass solution is 1:1, so as to obtain a material II; adding sodium hydroxide and sodium bicarbonate according to a mass ratio of 4:3 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH value of the system to be 7.5, aging for 1h at 65 ℃, filtering, and drying for 24h at 100 ℃ to obtain the product.
Example 3
Preparing Al with concentration of 15g 2 O 3 100mL of aluminum sulfate solution, adding 25g/100mL of sulfuric acid solution L, controlling pH=1 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 40 ℃; preparation of 20g SiO 2 100mL of silica sol solution, slowly dropwise adding the silica sol into the material I in a stirring state within 60min, wherein the volume ratio of the aluminum sulfate solution to the silica sol is 1:1.5, so as to obtain a material II; adding sodium hydroxide and sodium bicarbonate according to the mass ratio of 8:3 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH value of the system to be 8.0, aging for 2 hours at 65 ℃, filtering, and drying for 24 hours at 100 ℃ to obtain the product.
Example 4
Preparing Al with concentration of 20g 2 O 3 100mL of aluminum sulfate solution, adding sulfuric acid solution L with the concentration of 30g/100mL, controlling pH to be 2.5 to obtain a material I, and introducing circulating water to keepThe temperature of the material I is 35 ℃; preparation of 20g SiO 2 100mL of silica sol solution, slowly dropwise adding the silica sol into the material I in a stirring state within 60min, wherein the volume ratio of the aluminum sulfate solution to the silica sol is 1:1, so as to obtain a material II; adding sodium hydroxide and sodium bicarbonate according to the mass ratio of 8:5 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH value of the system to be 8.0, aging for 4 hours at 50 ℃, filtering, and drying for 24 hours at 90 ℃ to obtain the product.
Example 5
Preparing Al with concentration of 12g 2 O 3 Adding 25g/100mL nitric acid solution L into 100mL sodium metaaluminate solution, controlling pH=2 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 30 ℃; preparation of 8g SiO 2 100mL of sodium silicate solution, slowly dropwise adding the sodium silicate solution into the material I in a stirring state within 60min, wherein the volume ratio of the sodium metaaluminate solution to the sodium silicate solution is 1:3, and obtaining a material II; adding sodium hydroxide and sodium bicarbonate according to the mass ratio of 8:7 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH value of the system to be 8.0, aging for 1.5 hours at 65 ℃, filtering, and drying for 20 hours at 120 ℃ to obtain the product.
Example 6
Preparing Al with concentration of 10g 2 O 3 100mL of sodium metaaluminate solution, adding 25g/100mL of hydrochloric acid solution L, controlling pH=2 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 40 ℃; preparation of 15g SiO 2 100mL of silica sol solution, slowly dropwise adding the silica sol into the material I in a stirring state within 60min, wherein the volume ratio of the sodium metaaluminate solution to the silica sol solution is 1:2, and obtaining a material II; sodium hydroxide and sodium bicarbonate are added according to a mass ratio of 1:1 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH of the system to be=6.5, aging for 3.0h at 55 ℃, filtering, and drying for 20h at 120 ℃ to obtain the product.
Example 7
Preparing Al with concentration of 10g 2 O 3 100mL of sodium metaaluminate solution, adding phosphoric acid solution L with the concentration of 20g/100mL, controlling the pH value to be 3 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 30 ℃; preparation of 20g SiO 2 100mL of white carbon black solution, slowly dropwise adding the white carbon black into the material I in a stirring state within 60min, wherein the volume ratio of the sodium metaaluminate solution to the white carbon black solution is 1:1, and obtaining a material II; adding sodium hydroxide and sodium bicarbonate according to the mass ratio of 8:1 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH value of the system to be 8.0, aging for 3.0h at 50 ℃, filtering, and drying for 20h at 120 ℃ to obtain the product.
Comparative example 1
Preparing Al with concentration of 10g 2 O 3 100mL of aluminum sulfate solution, adding sulfuric acid solution L with the concentration of 20g/100mL, controlling the pH value to be 1 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 25 ℃; preparation of 10g SiO 2 100mL of water glass solution, dropwise adding the material I into the water glass solution in a stirring state within 60min, wherein the volume ratio of the aluminum sulfate solution to the water glass solution is 1:1, and obtaining a material II; sodium hydroxide and sodium bicarbonate are added according to the mass ratio of 2:1 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH value of the system to be 7.0, aging for 2.0h at 60 ℃, filtering, and drying for 24h at 100 ℃ to obtain the product.
Comparative example 2
Preparing Al with concentration of 35g 2 O 3 100mL of aluminum sulfate solution, adding sulfuric acid solution L with the concentration of 20g/100mL, controlling the pH value to be 1 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 25 ℃; preparation of 20g SiO 2 100mL of water glass solution, slowly dropwise adding the water glass into the material I in a stirring state within 60min, wherein the volume ratio of the aluminum sulfate solution to the water glass solution is 1:1, so as to obtain a material II; sodium hydroxide and sodium bicarbonate are added according to the mass ratio of 2:1 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH value of the system to be 7.0, aging for 2 hours at 60 ℃, filtering, and drying for 24 hours at 100 ℃ to obtain an XRD pattern of the product, wherein the diffraction peak of the alumina crystal phase appears, which indicates that the product contains the alumina crystal phase and is not completely amorphous silica-alumina.
Comparative example 3
Preparing Al with concentration of 10g 2 O 3 100mL of aluminum sulfate solution, adding sulfuric acid solution L with the concentration of 20g/100mL, controlling the pH value to be 1 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 25 ℃; preparation of 10g SiO 2 100mL of water glass solution, slowly dropwise adding the water glass into the material I in a stirring state within 60min, wherein the volume ratio of the aluminum sulfate solution to the water glass solution is 1:1, so as to obtain a material II; sodium hydroxide and sodium bicarbonate are added according to the mass ratio of 2:1 to prepare a mixed alkali solution.
Slowly and concurrently adding the mixed alkali solution and the material II into a reaction tank, controlling the pH value of the system to be 12.0, aging for 2 hours at 60 ℃, filtering, and drying for 24 hours at 100 ℃ to obtain the product.
Comparative example 4
Preparing Al with concentration of 10g 2 O 3 100mL of aluminum sulfate solution, adding sulfuric acid solution L with the concentration of 20g/100mL, controlling the pH value to be 1 to obtain a material I, and introducing circulating water to keep the temperature of the material I at 25 ℃; preparation of 10g SiO 2 100mL of water glass solution, slowly dropwise adding the water glass into the material I in a stirring state within 60min, wherein the volume ratio of the aluminum sulfate solution to the water glass solution is 1:1, so as to obtain a material II; weighing sodium hydroxide to prepare alkali liquor.
Slowly and concurrently adding alkali liquor and a material II into a reaction tank, controlling the pH value of a system to be 7.0, aging at 60 ℃ for 2.0h, filtering, and drying at 100 ℃ for 24h to obtain a product.
TABLE 1 physicochemical Properties of products obtained in examples and comparative examples
|
Example 1
|
Example 2
|
Example 3
|
Example 4
|
Example 5
|
Example 6
|
Specific surface area, m 2 /g
|
427.4
|
392.9
|
361.4
|
421.6
|
321.6
|
326.4
|
Pore volume, cm 3 /g
|
1.02
|
0.98
|
0.87
|
1.01
|
0.73
|
0.63
|
SiO 2 ,wt%
|
47.3
|
54.8
|
57.6
|
48.6
|
43.8
|
54.1 |
Table 1 shows the physicochemical properties of the products obtained in examples and comparative examples
|
Example 7
|
Comparative example 1
|
Comparative example 2
|
Comparative example 3
|
Comparative example 4
|
Specific surface area, m 2 /g
|
280.6
|
150.2
|
360.3
|
262.8
|
229.3
|
Pore volume, cm 3 /g
|
0.60
|
0.19
|
0.32
|
0.46
|
0.28
|
SiO 2 ,wt%
|
56.4
|
16.1
|
20.3
|
75.2
|
46.9 |
Example 8
The preparation method of the catalyst comprises the following steps: uniformly mixing amorphous silica-alumina, a Y molecular sieve, alumina, molybdenum oxide and nickel nitrate obtained in example 1, example 3, example 5 and comparative example 2 respectively, uniformly rolling powder under the action of an adhesive to prepare a hydrocracking catalyst, drying for 24 hours, putting into a muffle furnace, roasting for 4 hours at 500 ℃ to obtain hydrocracking catalysts 1-4 respectively, wherein the catalyst comprises the following components: amorphous silica alumina (20 wt%), Y molecular sieve (40 wt%), molybdenum oxide (16 wt%), nickel nitrate (4 wt%), alumina (balance). The hydrocracking catalyst 5 is prepared by uniformly mixing a Y molecular sieve, alumina, molybdenum oxide and nickel nitrate, uniformly rolling powder under the action of an adhesive, drying for 24 hours, putting into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the catalyst 5, wherein the catalyst comprises the following components: y molecular sieve (40 wt%), molybdenum oxide (16 wt%), nickel nitrate (4 wt%), alumina (balance).
Catalyst evaluation conditions: the hydrocracking catalyst was presulfided and then placed in a 200ml small hydrocracking apparatus. The properties of the raw oil used in the experiment are shown in table 2, and the evaluation process conditions are as follows: adopts a single-stage series once-through process flow, the reaction pressure is 10.0MPa, the liquid hourly space velocity (R1/R2) is 1.0/1.5h -1 The volume ratio of hydrogen to oil is 1200:1, and the organic nitrogen content of the raw oil in the hydrofining catalyst bed layer needs to be controlled<The comparative results of the reactivity of each catalyst at 5ppm and a controlled hydrocracking reaction conversion of 65% are shown in Table 3.
TABLE 2 oil Properties of raw materials
Density (20 ℃), g/cm 3 |
0.8430
|
Distillation range/. Degree.C
|
|
IBP/10%
|
215/279
|
50%/70%
|
321/332
|
95%/EBP
|
361/373
|
Condensation point/. Degree.C
|
32
|
S,wt%
|
1.31
|
N/μg·g -1 |
245
|
C/H,%
|
85.25/13.53
|
BMCI value
|
38.10 |
TABLE 3 catalyst product distribution
When the conversion rate of the hydrocracking reaction is controlled to be the same, the reaction temperature of the catalyst of the example is 5-11 ℃ lower than that of the catalyst of the comparative example, which shows that the reaction activity of the catalyst of the example is higher. In the product distribution, the heavy naphtha yields and C5 s obtained with the example catalysts + The total liquid yield is obviously higher than that of the catalyst of the comparative example. The amorphous silicon aluminum prepared by the method has better reactivity and selectivity performance of target products.