CN114272919A - Catalytic cracking assistant, preparation method and use method thereof - Google Patents
Catalytic cracking assistant, preparation method and use method thereof Download PDFInfo
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Abstract
The invention discloses a catalytic cracking auxiliary agent, a preparation method and a use method thereof. The catalytic cracking assistant comprises pseudo-boehmite, a heavy metal collector and clay, and is characterized by also comprising a mesoporous silicon-containing aluminum oxide material, wherein the mesoporous silicon-containing aluminum oxide material has an anhydrous chemical expression as follows by weight of oxides: (0-0.3) Na2O:(5‑25)SiO2:(80‑98)Al2O3(ii) a The ratio of B/L acid is 0.2-0.5 at 200 ℃; the mesoporous silicon-containing alumina material is characterized by TEM and has a net-shaped structure surface; the adding amount of the mesoporous silicon-containing aluminum oxide material is 5-25 parts by total mass of each component of the catalytic cracking auxiliary agent as 100 parts. The catalytic cracking assistant has the advantages of strong heavy oil conversion capability, high total liquid yield and the like.
Description
Technical Field
The invention relates to a catalytic cracking auxiliary agent, in particular to a catalytic cracking auxiliary agent, and a preparation method and a use method thereof.
Background
With the increasing trend of crude oil heaviness and deterioration worldwide, deep processing of heavy and poor crude oil becomes a major challenge for refineries to maximize profits of enterprises. Compared with the transformation of a catalytic cracking device and the development of a catalytic cracking catalyst, the development of the high-performance catalytic cracking auxiliary agent is the most economic and flexible effective means for a refinery to promote the deep conversion of heavy crude oil, improve the productivity and increase high-added-value products. The matrix is an important component of the catalytic cracking auxiliary agent, and the acidity and the pore structure of the matrix carrier need to be modulated in order to improve the cracking performance of heavy oil macromolecules.
US4749672 and US4836913 disclose a CLS/mullite carrier material which uses kaolin as a raw material and is calcined at a high temperature of about 1000 ℃ to produce a large amount of products with a silicon-aluminum spinel structure and a small amount of mullite structure. Then the macroporous cracking component with high activity and high stability is obtained by alkali extraction and ion exchange under the controlled condition. The carrier has better heavy oil cracking performance.
USP5051385 describes a method for synthesizing a mesoporous silicon-aluminum materialThe pore diameter is 20-50nm, the specific surface area is 50-100m2g-1. The aperture of the silicon-aluminum material prepared by CN03147975.8 is 10-20nm, and the pore volume can reach 1cm3g-1The above.
One of the main characteristics of a GO-ULTRA catalyst (NPRA,2010AM-10-175) newly introduced in Albemarle2009 is that the macroporous structure is greatly improved, the macropores of the catalyst are greatly increased within the range of 100-400nm, and the overcracking reaction, the excessive hydrogen transfer activity and the coke polymerization reaction are greatly reduced. Compared with a catalyst RUBY of GO-ULTRA of the same company, the GO-ULTRA has better coke selectivity while having high gasoline and diesel oil yields under the condition of the same catalyst-oil ratio, conversion rate and coke difference.
US 165083 reports that the addition of sucrose during the catalyst synthesis introduces macropores into the matrix, which improves the activity and heavy metal resistance of the catalyst. CN1778676A discloses a preparation method of an in-situ crystallization catalyst, which can effectively improve the pore structure of the catalyst by adding structural auxiliary agents of starch and carboxymethyl cellulose.
US4624773 reports a process for preparing a macroporous catalytic cracking aid using carbon black. At least 0.10cm can be generated by the introduction of carbon black3g-1The above macropores having a pore diameter of greater than 100 nm. The keemun tablet is prepared by adding polystyrene balls with different grain sizes and contents to synthesize macroporous catalytic cracking assistant, and it is found that the addition of polystyrene balls not only introduces mesopores, but also improves the activity of catalyst (Energy Fuels,24(5),2010,2825).
The DMS technology disclosed by ENGHARD is a simplified Distributed Matrix Structures technology, the particles have a card type stacking shape and a highly dispersed Matrix structure, meanwhile, highly dispersed zeolite crystals cover the surface of the Matrix to improve the selectivity of the catalyst, and in addition, a DMS product contains a stable mesoporous aluminum-rich carrier in order to improve the cracking capability of heavy oil. The aluminum-rich carrier is obtained by alkali-modified high-temperature roasting of kaolin (NPRA-AM-03-38).
For the current domestic catalytic cracking assistant, the acidity and the mesoporous structure of the matrix are mainly provided by activated alumina, and mainly comprise a double-aluminum matrix of pseudo-boehmite and aluminum sol. The skilled person therefore also often uses modified alumina to increase the pore structure of the catalyst.
Zhengjinyu, et al (Petroleum institute, 26 (6)), 2010 (846) adopts tetraethoxysilane to modify pseudo-boehmite, and obtains the silicon modified alumina material through acid catalytic reaction, temperature rise aging, filtering, washing, drying and high temperature roasting, the mesoporous pore volume is increased, but the pore diameter is not changed greatly. The method for preparing the silicon modified alumina has more steps and simultaneously uses an expensive organic silicon source.
CN03147975 discloses a medium pore silicon aluminium material suitable for catalytic cracking auxiliary agent, the material has pseudo-boehmite phase structure, anhydrous chemical expression based on oxide weight is: (0 to 0.3) Na2O·(40～90)Al2O3·(10～60)SiO2The specific surface area is 200-400 m2The pore volume is 0.5-2.0 ml/g, the average pore diameter is 8-20 nm, and the most probable pore diameter is 5-15 nm. The material is prepared by neutralizing an aluminum source and an alkali solution to form gel, then adding a silicon source, aging, and finally performing ion exchange, drying and roasting. The material has centralized mesopore distribution, retains the mesopore structure characteristic of alumina, has good hydrothermal stability, and has stronger macromolecule cracking capability, higher raw oil conversion rate and lower heavy oil yield when being used as a catalytic cracking auxiliary agent carrier compared with the prior silicon-aluminum material. The method has the disadvantages that the method adopts a sol-gel method to prepare the mesoporous silicon-aluminum, obtains the porous material by controlling the condensation between two ions of the aluminosilicate, adopts a low-concentration silicon source and an aluminum source to react, and has low product yield; the steps are complex, and the requirements on the pH value and the reaction temperature are high; because more anions and sodium ions are introduced, a large amount of water is needed for the ion exchange or washing process, and the water consumption is high.
Conventional catalytic cracking promoters are typically comprised of a matrix-containing carrier and a molecular sieve active component, whereas for heavy oil conversion promoters, they may be free of a molecular sieve active component since they are primarily directed to cracking heavy oil macromolecules. The company InterA in the United states introduced BCA-105 bottom oil cracking aid in the 90's of the 20 th century, which heavy oil cracking aid did not contain a zeolite component and used amorphous silicon aluminum having a certain activity and acidity.
CN99121917.1 discloses a catalytic cracking heavy oil cracking assistant, which is composed of alumina, clay and silica, wherein the content of alumina is 10-85 wt%, the content of clay is 10-85 wt%, the content of silica is 1-20 wt%, and the weight ratio of silica to alumina is 0.01-0.5. The assistant has high macromolecule cracking capability, and can be used together with a main catalyst containing zeolite to improve the conversion rate of heavy oil, reduce the yield of slurry oil and increase the yield of light oil.
An assistant for improving the yield of the residual oil catalytic cracking light oil is developed by Jinling petrochemical company (petroleum refining and chemical engineering, 2000, 31 (12): 8-11), a carrier of the assistant comprises four components of A1, Si, Mg and P, active components of the assistant select rare earth metals and transition metals, and the assistant has good residual oil cracking activity and strong hydrothermal stability.
CN201110026948.0 discloses a catalytic cracking composition and a catalytic cracking assistant, wherein the catalytic cracking composition contains 2-65 wt% of silica-magnesia gel, 1-25 wt% of rare earth compound and 15-85 wt% of diaspore.
Catalytic cracking promoters without zeolite components generally require large pore volumes and specific surface areas, good acid distribution.
CN201210061876.8 discloses a preparation method of catalytic cracking cocatalyst, which comprises: taking kaolin as a raw material, adding deionized water, mixing and pulping, adding a binder and a compound which is 1-10% of the kaolin by mass and has a decomposition or boiling point temperature of less than or equal to 150 ℃; spray drying the obtained slurry to prepare microspheres, and roasting the microspheres to obtain roasted microspheres; mixing the roasted microspheres with a silicon source, an alkali solution and a guiding agent, and then carrying out hydrothermal crystallization, filtration, washing and drying to obtain an in-situ crystallization product with the NaY zeolite content of 5-20%; and exchanging the in-situ crystallized product with ammonium salt, rare earth and magnesium salt, and roasting to obtain the catalytic cracking diesel oil cocatalyst. The patent introduces the mesoporosity during the catalyst spray drying process by introducing compounds which are decomposed and completely converted into gas at the boiling temperature of less than or equal to 150 ℃ or at 150 ℃ in the spray slurry.
To enhance the heavy oil conversion capability of the catalytic cracking assistant, the specific surface area of the matrix should be increased. The pseudoboehmite is an important component of the catalytic cracking matrix at present, however, after the pseudoboehmite is peptized, the viscosity is greatly increased, if the specific surface area of the matrix is increased by only increasing the content of the pseudoboehmite, the solid content of the slurry in the preparation process is greatly reduced, and the yield of the catalytic cracking auxiliary agent is influenced. Meanwhile, fine particles generated after peptization of the pseudo-boehmite can also block the pore channels of the catalytic cracking assistant. In addition, the alumina material using the traditional pseudoboehmite as the precursor still faces the problem that the acid amount is insufficient, only the L acid center is contained, and the B acid center is not existed, and the heavy oil conversion capability needs to be further improved. Researches show that the adsorption and reaction performance of the aluminum oxide material are related to the morphology of the aluminum oxide material besides the pore structure. In order to improve the adsorption or reaction properties of alumina, researchers have developed various shapes of alumina materials, including fibrous, sea urchin-like, spherical, flower-like, and the like. The research on modulating the surface acidity of the alumina, introducing the B acid center and preparing the alumina material with special morphology has important significance for the development of the catalytic cracking assistant.
Therefore, at present, pseudo-boehmite is directly used as a main component to prepare the catalytic cracking assistant, and the acid amount, acid distribution, pore volume, heavy oil conversion capacity and the like of the catalytic cracking assistant are still difficult to achieve ideal states.
Disclosure of Invention
The invention provides a catalytic cracking assistant and a preparation method thereof, wherein the catalytic cracking assistant has the characteristics of strong heavy oil conversion capability and high total liquid yield.
In order to achieve the purpose, the catalytic cracking assistant disclosed by the invention comprises pseudo-boehmite, a heavy metal collector and clay, and further comprises a mesoporous silicon-containing aluminum oxide material, wherein the mesoporous silicon-containing aluminum oxide material has an anhydrous chemical expression as follows by weight of oxides: (0-0.3) Na2O:(5-25)SiO2:(80-98)Al2O3(ii) a The ratio of B/L acid is 0.2-0.5 at 200 ℃; the mesoporous silicon-containing alumina material is characterized by TEM and has a net-shaped structure surface; to be provided withThe total mass of the components of the catalytic cracking auxiliary agent is 100 parts, and the adding amount of the mesoporous silicon-containing aluminum oxide material is 5-25 parts on a dry basis.
More specifically, the catalytic cracking assistant disclosed by the invention comprises 8-35 parts of pseudo-boehmite, particularly preferably 10-30 parts, calculated by the mass of alumina, based on 100 parts of the total mass of each component of the catalytic cracking assistant; the mesoporous silicon-containing alumina material is 5-25 parts by mass of a dry basis, and particularly preferably 8-20 parts by mass of a dry basis; the heavy metal trapping agent is 1-10 parts by mass of the metal oxide; on a dry basis, the clay accounts for 20-84 parts, preferably 30-79 parts; the mesoporous silicon-containing alumina material has the anhydrous chemical expression as follows based on the weight of oxides: (0-0.3) Na2O:(5-25)SiO2:(80-98)Al2O3(ii) a The ratio of B/L acid is 0.2-0.5 at 200 ℃; the mesoporous silicon-containing alumina material is characterized by TEM and has a net-shaped structure surface.
The invention discloses a catalytic cracking assistant, wherein the mesoporous silicon-containing alumina material is characterized by TEM, and the surface with a reticular structure is obtained by observing a sample by adopting a transmission electron microscope and imaging by utilizing the interaction of an electron beam and the sample to obtain a substance in a TEM picture of the sample with the reticular structure. The acid content of B acid and L acid at 200 ℃ is determined by adopting conventional pyridine absorption infrared spectroscopy (Py-FTIR) in the field (oil refining and chemical engineering, 2004,15 (4): 28-29; once amphiphilic), and the chemical property of the surface of the alumina carrier is opposite to Ni-W/gamma-Al2O3The research on the influence of the activity of the hydrogenation catalyst discloses the infrared spectroscopy for measuring the surface acidity of the solid acid catalyst. The test conditions of the invention are as follows: tabletting the sample, placing the sample in an infrared in-situ detection pool, and carrying out surface purification for two hours in a vacuum environment at 350 ℃ to remove gas molecules adsorbed in the sample; and cooling to room temperature, introducing pyridine steam, raising the temperature to 200 ℃ after balancing, vacuumizing, and desorbing in vacuum for 30 minutes to obtain a pyridine infrared spectrogram obtained by desorbing the sample at 200 ℃. According to 1540cm in the pyridine infrared spectrogram-1And 1450cm-1The characteristic absorption peak intensity calculates the ratio of B acid/L acid.
The catalytic cracking assistant disclosed by the invention has no special requirements, and can be a heavy metal collector commonly used in the field. For example, various heavy metal trapping agents are disclosed in petrochemical (2000, 29, (368-: magnesium oxide, strontium oxide, barium oxide, rare earth oxide, zirconium oxide, or the like, or precursors thereof. The invention preferably adopts magnesium oxide, magnesium oxide precursor, rare earth oxide and/or rare earth oxide precursor as the heavy metal collector. The precursor of the rare earth oxide precursor is preferably one or more of rare earth chloride, rare earth nitrate, rare earth carbonate and rare earth hydroxide. Wherein, the rare earth element can be one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.
The invention discloses a catalytic cracking assistant, wherein the clay is one or more of kaolin, halloysite, montmorillonite, bentonite, diatomite, sepiolite, attapulgite, rectorite, halloysite, hydrotalcite and soapstone. More preferably one or more of kaolin, halloysite, diatomite, sepiolite, attapulgite, rectorite and halloysite.
The catalytic cracking assistant disclosed by the invention can comprise other commonly used substrates, and the other commonly used substrates and the addition amount thereof are not particularly limited and are common knowledge in the field; the other commonly used substrates are generally selected from mixtures of one or more of alumina and its precursors, silica and its precursors, other than pseudoboehmite. The other alumina except the pseudo-boehmite is selected from one or more of alpha-alumina, beta-alumina, gamma-alumina, delta-alumina, eta-alumina and theta-alumina, and the alumina precursor is selected from one or more of alumina sol and aluminum hydroxide; the silicon oxide is selected from one or more of silica sol, silica gel, mesoporous silica, white carbon black and silica aerogel, and the silicon oxide precursor is selected from one or more of sodium silicate, sodium metasilicate, water glass and orthosilicate.
The invention discloses a catalytic cracking assistant, which is prepared by the following steps: uniformly mixing water, pseudo-boehmite and alkyl trimethyl quaternary ammonium salt type cationic surfactant, adding a Y-type zeolite guiding agent, mixing, homogenizing, and then heating to 60-100 ℃ for reaction; after the reaction is finished, filtering, washing, drying and roasting the obtained solid precipitate; wherein the addition amount of the alkyl trimethyl quaternary ammonium salt type cationic surfactant is 0.01-0.05 of the dry basis weight of the pseudo-boehmite; the addition amount of the Y-type guiding agent is 0.02-0.30 of the total mass of the pseudo-boehmite and the silicon-aluminum in the Y-type guiding agent calculated by silicon oxide.
The invention discloses a catalytic cracking assistant, wherein an alkyl trimethyl quaternary ammonium salt cationic surfactant is one of alkyl quaternary ammonium salt surfactants in the preparation method of a mesoporous silicon-containing alumina material, and the alkyl trimethyl quaternary ammonium salt cationic surfactant is structurally characterized in that three methyl groups and a non-methyl alkyl group are connected to a nitrogen atom, namely four hydrogen atoms of ammonium ions are completely replaced by three methyl groups and a non-methyl alkyl group. The alkyl is long-chain hydrocarbon alkyl, which can be straight-chain alkyl or branched-chain alkyl, and is preferably C10-C18 alkyl. The alkyl trimethyl quaternary ammonium salt type cationic surfactant is preferably one or more of cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium hydroxide, tetradecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride and dodecyl trimethyl ammonium hydroxide.
The invention discloses a catalytic cracking assistant, wherein the addition amount of alkyl trimethyl quaternary ammonium salt type cationic surfactant in the preparation method of the mesoporous silicon-containing alumina material is 0.01-0.05, preferably 0.02-0.04 of the pseudo-boehmite.
The invention discloses a catalytic cracking assistant, wherein the addition amount of a guiding agent in the preparation method of the mesoporous silicon-containing alumina material is 0.02-0.30, preferably 0.1-0.25 of the total mass of pseudo-boehmite and silicon and aluminum in the guiding agent in terms of silicon oxide.
The invention discloses a catalytic cracking assistant, wherein the preparation method of the mesoporous silicon-containing aluminum oxide material has the reaction temperature of 60-100 ℃ and the reaction time of 0.5-4 h; the reaction temperature is preferably 80 to 100 ℃.
In the preparation method of the mesoporous silicon-containing aluminum oxide material, the solid precipitate is dried and then treated by 100 percent of water vapor, specifically, the dried sample is treated by 100 percent of water vapor at the temperature of 100-300 ℃ for 1-5 h.
In the preparation method of the mesoporous silicon-containing alumina material disclosed by the invention, roasting is a conventional technical means in the field, and the invention is preferably roasted at the temperature of 450-650 ℃, wherein the roasting time is 0.5-5 h. The calcination may be carried out in the presence of 0 to 100% water vapor.
The invention discloses a catalytic cracking assistant, wherein a Y-type zeolite guiding agent in the preparation method of a mesoporous silicon-containing aluminum oxide material is not particularly limited, and a common guiding agent is adopted, for example, the composition molar ratio of the guiding agent is (14-16) SiO2:(0.7～1.3)Al2O3:(14～16)Na2O:(300～330)H2O, prepared according to the method described in CN 1081425A.
The invention discloses a catalytic cracking assistant, wherein in the preparation method of the mesoporous silicon-containing aluminum oxide material, solid precipitate is filtered and washed for removing sodium ions, and can be washed for multiple times for achieving a better effect, and ammonium exchange and/or acid exchange can be carried out after washing for removing impurity ions. As long as the requirement of a sodium content of less than 0.3 wt% is met. The ammonium exchange or acid exchange method for removing impurity ions is a common technical means in the field, namely, the material is treated in an aqueous solution containing ammonium ions/hydrogen radical ions for a period of time, so that the impurity ions in the material and the ammonium ions or the hydrogen ions are subjected to exchange reaction, and the content of the impurity ions in the material is reduced. In order to better achieve the reaction effect expected by the present invention, the preparation of the mesoporous silica-containing alumina material is recommended to be carried out ammonium exchange and/or acid exchange at 60-100 ℃ after washing. The ammonium exchange recommends the use of the following process conditions: the solid precipitate was separated as a precipitate (dry basis): ammonium salt: h2O＝1：(0.1-1): (5-10) exchanging the weight ratio at 60-100 ℃; exchanging for 1-3 times, each time for 0.3-1 hour, until the sodium content in the solid precipitate is less than 0.3 wt%. The ammonium salt used for exchange is selected from one or more of ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium sulfate and ammonium bicarbonate. The acid exchange recommends the use of the following process conditions: the solid precipitate was separated as a precipitate (dry basis): h2O is 1: (5-10) mixing, adjusting the pH to 2.5-3.5 with an acid solution, and exchanging at 60-100 ℃; exchanging for 1-3 times, each time for 0.3-1 hour, until the sodium content in the solid precipitate is less than 0.3 wt%. The acid solution used for exchange is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and citric acid solution.
In the preparation method of the mesoporous silicon-containing aluminum oxide material, the drying is a general technology and can be carried out in an oven or a spray drying or flash drying mode.
The invention also discloses a preparation method of the catalytic cracking auxiliary agent, which comprises the following steps: mixing and pulping pseudo-boehmite, a mesoporous silicon-containing alumina material, a heavy metal trapping agent and clay, molding and drying.
The preparation method of the catalytic cracking assistant disclosed by the invention comprises the acidification process commonly used in the field, can be used for acidifying any material containing pseudo-boehmite before mixing and pulping, and can also be used for acidifying after mixing and pulping after all materials are added.
The preparation method of the catalytic cracking assistant disclosed by the invention has no special limitation on the adding sequence of the pseudo-boehmite and other materials.
The preparation method of the catalytic cracking assistant disclosed by the invention is characterized in that the forming and drying refers to granulation forming and drying of the catalytic cracking assistant, which are techniques known to technicians in the field, the preparation of the catalytic cracking assistant generally adopts spray forming and drying, and the process conditions are that the temperature of a hearth of a spray tower is controlled to be 450-550 ℃, and the temperature of spray tail gas is controlled to be 150-300 ℃.
The invention discloses a preparation method of a catalytic cracking auxiliary agent and a catalytic cracking product prepared by the preparation methodThe chemical assistant can be further treated by ion exchange, and the ion exchange can remove various impurity ions, including Na, brought by various links in the preparation of the catalytic cracking assistant+，SO4 2-，Cl-And the like, and usually a large amount of water washing or ammonium salt water washing is employed under acidic conditions. The process conditions of the ion exchange recommended by the invention are as follows: the ion exchange adopts acid exchange or ammonium exchange, the pH value is 2.5-3.5, and the exchange time is 0.3-2 hours.
The invention also discloses a using method of the catalytic cracking auxiliary agent, which comprises the following steps: the catalytic cracking auxiliary agent and the catalytic cracking catalyst are jointly used for catalytic cracking reaction. The addition mode of the catalytic cracking auxiliary agent on the device is generally two, one mode is that the catalytic cracking auxiliary agent and the catalytic cracking catalyst are mixed in advance and then enter a catalytic cracking reaction-regeneration system; the other is that the catalytic cracking catalyst and the catalytic cracking auxiliary agent are respectively added into a catalytic cracking reaction-regeneration system.
The catalytic cracking assistant disclosed by the invention has higher pore volume, higher acid amount and higher B/L acid ratio compared with the traditional alumina material due to the introduction of the alumina material with a reticular structure and B/L acid mesopores, and has stronger heavy oil macromolecule conversion capability and total liquid yield increasing effect compared with the conventional method when being applied to the catalytic cracking assistant. The preparation method of the catalytic cracking auxiliary agent is based on the use of cheap silicon-aluminum sources, obtains the silicon-containing aluminum oxide material with higher B/L acid ratio and a reticular structure by a post-modification method, and then prepares the auxiliary agent, thus having wider industrial application prospect.
Drawings
FIG. 1 shows a silicon-containing alumina material and γ -Al prepared in example 32O3(the raw material pseudo-boehmite is roasted for 2h at the temperature of 550 ℃) in the presence of a catalyst. The characteristic peaks appear at 35-40 degrees, 45 degrees and 67 degrees of 2 theta, which are indicated as gamma-Al2O3And (4) a crystalline state.
Fig. 2 is a TEM picture of the silicon-containing alumina material prepared in example 3, showing a network surface structure.
Fig. 3 is a TEM picture of the silicon-modified alumina material prepared in comparative example 1, which shows that the material is a nanoparticle stacking structure.
Detailed Description
The effects of the present invention are further illustrated by the following examples. It should be understood, however, that the following examples are not intended to limit the scope of the present invention, and that any modifications that do not depart from the spirit and scope of the present invention are intended to be within the scope of the present invention.
1. Raw materials
NaY zeolite guiding agent, produced by catalyst factory of Lanzhou petrochemical company;
kaolin, an industrial product of Kaolin corporation, China, by an amount of 20.43% as appropriate;
pseudo-boehmite, produced by Shanxi aluminum plant, is reduced by 31.5 percent;
aluminium sol containing Al2O320.4 wt%, produced by catalyst works of landification corporation, Lanzhou;
silica sol containing Al2O330.6 wt%, produced by catalyst factory of landish petrochemical company;
mixed rare earth solution with the content of oxidized rare earth of 325g/l, produced by catalyst factories of Lanzhou petrochemical company;
magnesium oxide, analytical pure, Mimi European chemical reagent Co., Tianjin;
lanthanum chloride and cerium chloride, both of which are obtained by the research institute of optochemical and fine chemical industry in Tianjin, are analytically pure and are respectively prepared into lanthanum chloride and cerium chloride solutions with the content of rare earth oxide of 300g/l for use.
2. Analytical method
In each example, Na is present in the product2O、A12O3、SiO2The content of (A) was measured by X-ray fluorescence (see "analytical methods in petrochemical industry (RIPP methods of experiments)", eds., Yanggui et al, published by scientific Press, 1990). The specific surface and the pore structure are measured by a low-temperature nitrogen adsorption-desorption method. TEM was carried out on a transmission electron microscope of JEM 2010 type manufactured by JEOL, a Japanese Electron corporation, operating at a voltage of 200 kv.
Pyridine absorption Infrared Spectroscopy (Py-FTIR) the sample acid type was characterized by Fourier transform Infrared Spectroscopy model TENSOR-27, manufactured by Bruker, USA. The 10mg samples were tableted and placed in an in situ cell, surface cleaned for two hours at 350 ℃ in a vacuum environment and then subjected to infrared analysis.
Light oil micro-reverse test: on a WF-2006 fixed fluidized bed micro-reactor manufactured by Beijing Huayang company, the micro-reaction activity evaluation is carried out on the catalytic cracking auxiliary agent by taking Hongkong light diesel oil as a raw material. The evaluation conditions were: the reaction temperature is 460 ℃, the reaction time is 70s, the loading amount of the catalytic cracking assistant is 5g, and the oil inlet amount of the diesel oil is 1.56 g. After the reaction, the gasoline yield was measured by GC-7890 type chromatography manufactured by Agilent, USA.
Abrasion index test method:
the abrasion strength of the catalytic cracking assistant is measured by a gas generation method: the catalytic cracking auxiliary agent is placed in an MS-C type abrasion index analyzer of a device for measuring the abrasion index, airflow impact is carried out for 5 hours, the amount of the fine powder collected in the first 1 hour is the amount of the fine powder contained in the preparation of the catalytic cracking auxiliary agent, the amount of the fine powder collected in the last 4 hours is used as the amount of the generated fine powder (less than 15 mu m), and the percentage of the mass of the fine powder collected in the last 4 hours in the total mass of the sample is the abrasion index.
Pore volume measurement by water drop method:
and (2) putting about 80g of a catalytic cracking assistant sample into an evaporation dish, igniting for 1 hour at 480 ℃, taking out the sample, cooling the sample in a drier, and adding 20g of the sample into a triangular flask to the accuracy of 0.1 g. Adding distilled water into a triangular flask through a burette, wherein the fluidity of the catalytic cracking assistant is deteriorated along with the addition of water, continuously stirring and shaking the mixture by a glass rod until the sample loses fluidity and is completely polymerized together, recording the water consumption, and calculating the pore volume of the sample by adopting Vp ═ V/m. Vp-sample pore volume, ml/g; v-consumption of titration water volume, ml; m-sample mass, g.
3. Evaluation of catalytic cracking assistant:
the catalytic cracking auxiliary agent and the comparative catalytic cracking auxiliary agent are respectively physically mixed and compounded with an industrial catalyst LDO-75 according to the weight ratio of 1:5, after mixing, the mixture is aged for 17 hours by 100 percent of water vapor at 800 ℃ and then is evaluated by an ACE device, the used raw oil is Xinjiang vacuum wide-cut wax oil and Xinjiang vacuum residual oil, and the slag doping ratio is 30%. The properties of the feed oil are shown in Table 1. After mixing the catalytic cracking catalyst and the auxiliary agent, carrying out aging for 17h at 800 ℃ by 100 percent of water vapor, and then carrying out reaction performance evaluation.
TABLE 1 Selective evaluation of the Properties of the raw oils used
Preparation of a guiding agent: weighing quantitative sodium aluminate, sodium hydroxide, water and water glass according to the proportion of 16SiO2:1Al2O3:16Na2O:320H2And mixing O uniformly, then heating to 34 ℃, and aging for 24h at the temperature to obtain the NaY zeolite directing agent.
The technical solution of the present invention will be further illustrated by the following examples.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
In each embodiment, physicochemical data of specific surface, pore structure and the like are measured by a low-temperature nitrogen adsorption-desorption method.
Example 1
Preparation of silicon-containing alumina
Placing 550ml of deionized water in a beaker, adding 100g (dry basis, the same below) of pseudo-boehmite and 3.5g of hexadecyl trimethyl ammonium bromide under the stirring condition, stirring for 60min, and adding a prepared directing agent solution, wherein the adding amount of the directing agent is 0.17 of the total mass of the pseudo-boehmite and the silicon-aluminum of the directing agent calculated by silicon oxide; stirring for 30min, then heating to 100 ℃, continuing to react for 3h under stirring, filtering and washing the obtained product, and then obtaining a solid precipitate (dry basis): ammonium nitrate: water 1: 0.4: 7 mixing, performing acid exchange at 85 ℃ to remove sodium ions, repeating the exchange twice for 0.3h, performing water washing filtration after each exchange, and drying at 150 ℃ for 8 h. And (3) treating the dried sample by 100% water vapor at 180 ℃ for 2.0h, and then roasting at 640 ℃ for 1.0h to obtain the mesoporous silicon-containing alumina material LS-1 provided by the invention. The pore structure, B/L, of the material is shown in Table 2.
Preparation of catalytic cracking assistant
1.847 kg of kaolin was weighed, 5.2 kg of deionized water was added, 0.876 kg of pseudo-boehmite, 1.471 kg of alumina sol, LS-1510 g (dry basis, the same applies hereinafter) of mesoporous silica-containing alumina material and 369.2ml of rare earth solution were added with stirring, stirred for 30 minutes, then 155 ml of 37 wt% hydrochloric acid was added, stirred for 45 minutes, aged at 70 ℃ for 40 minutes and spray-dried.
Roasting the catalytic cracking assistant obtained by spray drying at 550 ℃ for 2h, then stirring in a hydrochloric acid aqueous solution with the pH value of 3.2 for 40 minutes, filtering, and drying at 130 ℃ for 8 hours to obtain the cracking catalytic cracking assistant A-1 provided by the invention.
The catalytic cracking assistant A-1 comprises the following components: 49% by weight of kaolin, 20% by weight of alumina from pseudoboehmite, 10% by weight of alumina from alumina sol, 17% by weight of mesoporous siliceous alumina and 4% by weight of rare earth oxide.
Example 2
Preparation of silicon-containing alumina
Placing 800ml of deionized water in a beaker, adding 100g of pseudo-boehmite and 1.5g of tetradecyl trimethyl ammonium bromide under the stirring condition, stirring for 45min, and adding a prepared directing agent solution, wherein the addition amount of the directing agent is 0.03 of the total amount of the pseudo-boehmite and the silicon-aluminum serving as the directing agent, calculated by silicon oxide; stirring for 100min, then heating to 85 ℃, continuing to react for 0.5h under stirring, filtering and washing the obtained product, and then obtaining a solid precipitate (dry basis): mixing water 1:5, adjusting the pH value to 3.0 by hydrochloric acid, performing ion exchange at 75 ℃ to remove sodium ions, exchanging for 0.5h, performing water washing and filtering after the exchange is finished, drying for 16h at 125 ℃, treating a sample with 100% water vapor at 250 ℃ for 4.3h after the drying, and then roasting for 2.4h at 560 ℃ to obtain the mesoporous silicon-containing alumina material LS-2 provided by the invention. The pore structure, B/L, of the material is shown in Table 2.
Preparation of catalytic cracking assistant
2.463 kg of kaolin was weighed, 6.5 kg of deionized water was added, 0.876 kg of pseudo-boehmite, 1.569 kg of alumina sol, 2800 g of mesoporous silica-containing alumina material LS-2800 g and 1066.7ml of lanthanum chloride solution were added with stirring for 45 minutes, followed by addition of 172 ml of 37 wt% hydrochloric acid, stirring for 30 minutes, aging at 60 ℃ for 1 hour, and spray-drying.
And roasting the catalytic cracking aid obtained by spray drying at 650 ℃ for 2h, then stirring in a hydrochloric acid aqueous solution with the pH of 2.8 for 20 minutes, filtering, and drying at 140 ℃ for 7 hours to obtain the catalytic cracking aid A-2 provided by the invention.
The catalytic cracking assistant A-2 comprises the following components: 49% by weight of kaolin, 15% by weight of alumina from pseudoboehmite, 8% by weight of alumina from alumina sol, 20% by weight of mesoporous siliceous alumina and 8% by weight of rare earth oxide.
Example 3
Preparation of silicon-containing alumina
Placing 400ml of deionized water in a beaker, adding 100g of pseudo-boehmite under the stirring condition, stirring for 30min, adding 4g of hexadecyl trimethyl ammonium chloride, and adding a prepared directing agent solution, wherein the addition amount of the directing agent is 0.23 of the total amount of the pseudo-boehmite and the directing agent silicon-aluminum; stirring for 1.2 h; and then heating to 95 ℃, continuously reacting for 1h under stirring, filtering and washing the obtained product, and mixing the obtained solid precipitate according to the weight ratio of the solid precipitate (dry basis): ammonium sulfate: mixing water 1:0.8:10, performing ion exchange at 80 ℃ to remove sodium ions, performing exchange for 0.75h, washing and filtering after the exchange is finished, drying at 110 ℃ for 18h, treating a sample with 100% of water vapor at 100 ℃ for 1.5h after the drying, and then roasting at 600 ℃ for 4.5h to obtain the mesoporous silicon-aluminum material LS-3 provided by the invention. The pore structure, B/L, of the material is shown in Table 2.
Preparation of catalytic cracking assistant
2.463 kg of kaolin was weighed, 7.8 kg of deionized water was added, 1.533 kg of pseudo-boehmite, 0.343 kg of alumina sol, 0.229 kg of silica sol, LS-3280 g of mesoporous silica-containing alumina material, and 215.4ml of rare earth solution were added with stirring, stirred for 60 minutes, followed by addition of 240 ml of 37 wt% hydrochloric acid, stirred for 90 minutes, aged at 55 ℃ for 90 minutes, and spray-dried.
Roasting the catalytic cracking assistant obtained by spray drying at 500 ℃ for 2h, then stirring in a hydrochloric acid aqueous solution with the pH value of 3.5 for 60 minutes, filtering, and drying at 110 ℃ for 12 hours to obtain the catalytic cracking assistant A-3 provided by the invention.
The catalytic cracking assistant A-3 comprises the following components: 56% by weight of kaolin, 30% by weight of alumina derived from pseudo-boehmite, 2% by weight of alumina derived from alumina sol, 2% by weight of silica derived from silica sol, 8% by weight of mesoporous silica-containing alumina, and 2% by weight of rare earth oxide.
Comparative example 1
Preparation of silicon-containing alumina
Comparative examples were prepared according to the Petroleum institute (Petroleum processing), 26(6), 2010, 846-. Placing 400ml of deionized water in a beaker, adding 100g of pseudo-boehmite under the stirring condition, stirring for 30min, adding hydrochloric acid with the mass fraction of 36% into the slurry according to a certain acid/aluminum mass ratio of 0.12, stirring for 5min, and adding an ethyl orthosilicate solution, wherein the ethyl orthosilicate is 0.23 of the total amount of the pseudo-boehmite and the ethyl orthosilicate silicon-aluminum calculated by silicon oxide; stirring for 1.2 h; the temperature was then raised to 95 ℃ and the reaction was continued for 1h with stirring. Then standing for 24h at 25 ℃, filtering and washing the obtained product, and then adding the obtained solid precipitate into a solid precipitate (dry basis): ammonium sulfate: mixing water at a ratio of 1:0.8:10, performing ion exchange at 80 ℃ to remove sodium ions, performing exchange for 0.75h, performing water washing filtration after the exchange is finished, drying at 110 ℃ for 18h, and then roasting at 600 ℃ for 4.5h to obtain the silicon modified alumina material DLS-1. The pore structure, B/L, of the material is shown in Table 2.
Preparation of catalytic cracking assistant
2.463 kg of kaolin was weighed, 7.8 kg of deionized water was added, 1.533 kg of pseudoboehmite, 0.343 kg of alumina sol, 0.229 kg of silica sol, DLS-1280 g of rare earth solution and 215.4ml of rare earth solution were added with stirring, and stirred for 60 minutes, followed by addition of 240 ml of 37% by weight hydrochloric acid, stirring for 90 minutes, aging at 55 ℃ for 90 minutes and spray-drying.
Roasting the catalytic cracking assistant obtained by spray drying at 500 ℃ for 2h, then stirring in a hydrochloric acid aqueous solution with the pH value of 3.5 for 60 minutes, filtering, and drying at 110 ℃ for 12 hours to obtain the catalytic cracking assistant DA-1 provided by the invention.
The catalytic cracking assistant DA-1 comprises the following components: 56% by weight of kaolin, 30% by weight of alumina derived from pseudo-boehmite, 2% by weight of alumina derived from alumina sol, 2% by weight of silica derived from silica sol, 8% by weight of DLS-1 and 2% by weight of rare earth oxide.
Example 4
Preparation of silicon-containing alumina
Placing 300ml of deionized water in a beaker, adding 100g of pseudo-boehmite and 4.5g of dodecyl trimethyl ammonium hydroxide under the stirring condition, stirring for 50min, adding a prepared directing agent solution, wherein the addition amount of the directing agent is 0.10 of the total amount of the pseudo-boehmite and the silicon-aluminum serving as the directing agent, calculated as silicon oxide; stirring for 60min, then heating to 60 ℃, continuing to react for 2.5h under stirring, filtering and washing the obtained product, and then obtaining a solid precipitate (dry basis): ammonium chloride: mixing water 1:1.0:6, performing ion exchange at 95 ℃ to remove sodium ions, repeating the exchange once for 0.6h each time, performing water washing and filtering after each exchange, drying at 130 ℃ for 10h, treating a sample with 100% water vapor at 200 ℃ for 2.8h after drying, and then roasting at 530 ℃ for 2.0h to obtain the mesoporous silicon-containing alumina material LS-4 provided by the invention. The pore structure, B/L, of the material is shown in Table 2.
Preparation of catalytic cracking assistant
3.645 kg of kaolin clay was weighed, 8.1 kg of deionized water was added, 0.730 kg of pseudo-boehmite, 1.961 kg of alumina sol, 0.654 kg of silica sol, LS-4700 g of mesoporous silica-containing alumina material, 100g of solid magnesium oxide, 666.7ml of cerium chloride solution were added with stirring, 80 minutes of stirring was carried out, 140 ml of 37% by weight hydrochloric acid was added, 60 minutes of stirring was carried out, aging was carried out at 65 ℃ for 80 minutes, and spray drying was carried out.
Roasting the catalytic cracking assistant obtained by spray drying at 620 ℃ for 2h, then stirring in a hydrochloric acid aqueous solution with the pH value of 3.3 for 60 minutes, filtering, and drying at 100 ℃ for 18 hours to obtain the catalytic cracking assistant A-4 provided by the invention.
The catalytic cracking assistant A-4 comprises the following components: 58% by weight of kaolin, 10% by weight of alumina from pseudo-boehmite, 8% by weight of alumina from alumina sol, 4% by weight of silica from silica sol, 14% by weight of mesoporous silica-containing alumina, 2% by weight of magnesia and 2% by weight of rare earth oxide.
Example 5
Preparation of silicon-containing alumina
Placing 850ml of deionized water in a beaker, adding 100g of pseudo-boehmite and 2.5g of tetradecyl trimethyl ammonium chloride under the stirring condition, stirring for 25min, and adding a prepared directing agent solution, wherein the addition amount of the directing agent is 0.20 of the total amount of the pseudo-boehmite and the silicon-aluminum serving as the directing agent, calculated by silicon oxide; stirring for 90min, then heating to 92 ℃, continuing to react for 3.5h under stirring, filtering and washing the obtained product, and mixing the obtained solid precipitate according to the weight ratio of the solid precipitate (dry basis): mixing water 1:9, adjusting the pH value to 2.8 by using citric acid, performing acid exchange at 100 ℃ to remove sodium ions, repeating the exchange once for 1.0h each time, performing water washing and filtering after each exchange, drying at 135 ℃ for 14h, treating a sample with 100% water vapor at 150 ℃ for 3.2h after drying, and then roasting at 480 ℃ for 3.8h to obtain the mesoporous silicon-containing alumina material LS-5 provided by the invention. The pore structure, B/L, of the material is shown in Table 2.
Preparation of catalytic cracking assistant
2.658 kg of kaolin clay is weighed, 9.3 kg of deionized water is added, 1.642 kg of pseudo-boehmite, 1.544 kg of alumina sol, 1.5647 g of mesoporous silicon-containing alumina material LS-5647 g, 135 g of solid magnesium oxide and 969.2ml of rare earth solution are added with stirring, 100 minutes of stirring is carried out, 241 ml of 37 weight percent hydrochloric acid is added, and after 70 minutes of stirring, the mixture is aged at 50 ℃ for 110 minutes and then spray-dried.
And roasting the catalytic cracking assistant obtained by spray drying at 600 ℃ for 1h, then stirring in a hydrochloric acid aqueous solution with the pH value of 3 for 30 minutes, filtering, and drying at 120 ℃ for 6 hours to obtain the catalytic cracking assistant A-5 provided by the invention.
The catalytic cracking assistant A-5 comprises the following components: 47% by weight of kaolin, 25% by weight of alumina from pseudo-boehmite, 7% by weight of alumina from alumina sol, 11% by weight of mesoporous siliceous alumina, 3% by weight of magnesium oxide and 7% by weight of rare earth oxide.
TABLE 2 physicochemical Properties of the different samples
TABLE 3 microreactivity of different samples
TABLE 4 physical and chemical Properties of catalytic cracking auxiliary
| Composition (wt%) | A-1 | A-2 | A-3 | A-4 | A-5 | DA-1 |
| Kaolin clay | 49 | 49 | 56 | 58 | 47 | 56 |
| Pseudo-boehmite (alumina meter) | 20 | 15 | 30 | 10 | 25 | 30 |
| Aluminium sol (alumina meter) | 10 | 8 | 2 | 8 | 7 | 2 |
| Silica sol (silica meter) | - | - | 2 | 4 | - | 2 |
| Magnesium oxide | - | - | - | 2 | 3 | - |
| Rare earth element | 4 | 8 | 2 | 4 | 7 | 2 |
| Mesoporous siliceous alumina | 17 | 20 | 8 | 14 | 11 | 8 |
| Abrasion index, m% | 1.2 | 1.5 | 1.9 | 1.7 | 1.6 | 2.1 |
| Pore volume, ml/g | 0.45 | 0.47 | 0.38 | 0.42 | 0.40 | 0.36 |
Pore volume was determined by water drop method
TABLE 5 evaluation data of ACE reaction after compounding catalytic cracking auxiliary agent with industrial agent LDO-75, respectively
The evaluation result of the ACE catalytic cracking experimental device shows that: after the A-3 catalytic cracking assistant is compounded with the industrial agent LDO-75 according to the ratio of 1:5, compared with the compounding of the catalytic cracking assistant in a comparative example 1, after the mesoporous silicon-containing alumina material is adopted, the heavy oil conversion is enhanced, the slurry oil yield is reduced by 0.99 percent, the total liquid yield is increased by 1.42 percent, and good reaction performance is shown.
Claims (12)
1. The catalytic cracking assistant comprises pseudo-boehmite, a heavy metal collector and clay, and is characterized by also comprising a mesoporous silicon-containing alumina material; the anhydrous chemical expression of the mesoporous silicon-containing alumina material is as follows based on the weight of oxides: (0-0.3) Na2O:(5-25)SiO2:(80-98)Al2O3The ratio of B/L acid at 200 ℃ is 0.2-0.5; the mesoporous silicon-containing alumina material is characterized by TEM and has a net-shaped structure surface; the addition amount of the mesoporous silicon-containing aluminum oxide material is 5-25 parts by dry basis based on 100 parts by total mass of the components of the catalytic cracking assistant.
2. The catalytic cracking assistant according to claim 1, wherein the catalytic cracking assistant comprises the following components by weight based on 100 parts of the total mass of the components: based on the mass of alumina, the mass of the pseudo-boehmite is 8-35 parts; on a dry basis, the mesoporous silicon-containing alumina material accounts for 5-25 parts; the heavy metal trapping agent is 1-10 parts by mass of the metal oxide; on a dry basis, 20-84 parts of clay.
3. The catalytic cracking aid according to claim 2, wherein the addition amount of each component is: 10-30 parts of pseudo-boehmite; 8-20 parts of mesoporous silicon-containing alumina material; 1-10 parts of a heavy metal trapping agent; 30-79 parts of clay.
4. The catalytic cracking aid according to claim 1, wherein the heavy metal trap is at least one selected from the group consisting of magnesium oxide, strontium oxide, barium oxide, rare earth oxide, and zirconium oxide.
5. The catalytic cracking aid according to claim 1, further comprising at least one of alumina and its precursor, silica and its precursor other than pseudoboehmite.
6. The catalytic cracking aid of claim 1, wherein the mesoporous silica-containing alumina material is prepared by a method comprising: uniformly mixing water, pseudo-boehmite and alkyl trimethyl quaternary ammonium salt type cationic surfactant, adding a Y-type zeolite guiding agent, mixing, homogenizing, and then reacting at the reaction temperature of 60-100 ℃ for 0.5-4h to obtain a solid precipitate; after the reaction is finished, filtering, washing, drying and roasting the obtained solid precipitate; wherein the addition amount of the alkyl trimethyl quaternary ammonium salt type cationic surfactant is 0.01-0.05 of the dry basis weight of the pseudo-boehmite; the addition amount of the Y-type guiding agent is 0.02-0.30 of the total mass of the pseudo-boehmite and the silicon-aluminum in the Y-type guiding agent calculated by silicon oxide.
7. The catalytic cracking assistant of claim 6, wherein the alkyl group of the alkyl trimethyl quaternary ammonium salt cationic surfactant is a C10-C18 linear alkyl group or a C10-C18 branched alkyl group.
8. The catalytic cracking aid according to claim 7, wherein the alkyl trimethyl quaternary ammonium salt type cationic surfactant is at least one selected from the group consisting of cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium hydroxide, tetradecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride and dodecyl trimethyl ammonium hydroxide.
9. The catalytic cracking aid according to claim 6, wherein the alkyl trimethyl quaternary ammonium salt type cationic surfactant is added in an amount of 0.02 to 0.04; the addition amount of the Y-type guiding agent is 0.1-0.25.
10. The catalytic cracking aid according to claim 6, wherein the reaction temperature is 80-100 ℃.
11. A process for preparing a catalytic cracking aid according to any one of claims 1 to 10, comprising: mixing and pulping pseudo-boehmite, a mesoporous silicon-containing alumina material, a heavy metal trapping agent and clay, molding and drying.
12. A method of using the catalytic cracking assistant according to any one of claims 1 to 10, wherein the catalytic cracking assistant and the catalytic cracking catalyst are used together in a catalytic cracking reaction.
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| CN117046506B (en) * | 2023-10-11 | 2023-12-08 | 山东久元新材料有限公司 | Oil refining powder solid auxiliary agent and preparation method thereof |
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