CN116212934A - Method for improving catalytic cracking catalyst activity - Google Patents
Method for improving catalytic cracking catalyst activity Download PDFInfo
- Publication number
- CN116212934A CN116212934A CN202111466703.XA CN202111466703A CN116212934A CN 116212934 A CN116212934 A CN 116212934A CN 202111466703 A CN202111466703 A CN 202111466703A CN 116212934 A CN116212934 A CN 116212934A
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- catalytic cracking
- cracking catalyst
- improving
- catalyst according
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Images
Classifications
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- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention relates to a method for improving the activity of a catalytic cracking catalyst, which comprises the following steps: (1) Mixing a magnesium source, a silicon source and an aluminum source, and aging to obtain a magnesium-silicon-aluminum material; (2) Mixing and pulping the magnesia-silica-alumina material with kaolin, seed crystal, water, dispersing agent and/or reinforcing agent, spraying, roasting and in-situ crystallization to obtain a crystallized product; (3) Introducing the crystallized product after roasting into a downstream bed isomorphous substitution reactor to be in countercurrent contact with silicon tetrachloride for isomorphous substitution reaction; and (4) performing an acid exchange and/or a rare earth ion exchange, the acid exchange or rare earth ion exchange being performed before the isomorphous substitution reaction or after the isomorphous substitution reaction. The catalyst prepared by the method has the advantages of more developed strong acid, high activity and more excellent performance.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a method for improving the activity of a catalytic cracking catalyst.
Background
The catalytic cracking catalyst activity is an important assessment index for the application of the catalyst in a catalytic cracking device, and in the case of heavy oil catalytic cracking catalysts, along with the increasing heavy weight, poor quality and severe environmental regulations of raw oil of an FCC device, the catalytic cracking catalyst is required to have more excellent reaction activity and performance.
In order to provide the catalytic cracking catalyst with excellent activity and reaction selectivity, early US4493902, 46976583a prepared porous precursor microspheres by using kaolin and sodium silicate binder, and preparing a high-activity catalyst by using a crystallized product with high molecular sieve content; EP 01973385a uses on this basis hydrous kaolin of smaller size than in the prior art as the specific calcined aluminum feedstock for the non-zeolite component (matrix) of the catalyst. The catalyst disclosed in CN 02820780.7 is also added with spinel, mullite and other materials selectively to raise the activity of the catalyst and promote the conversion of heavy oil in the material. After the crystallization product with high molecular sieve content is prepared by the earlier patent, the final catalyst is obtained by modification through a complicated post-modification process, the ammonia nitrogen pollution is serious, and the process implementation flow is long. CN201110208801.3 is sprayed withDeionized water and a compound with a decomposition or boiling point temperature less than or equal to 150 ℃ are added in the mist beating stage, an in-situ crystallization process is utilized to obtain an in-situ crystallization product, and then an in-situ crystallization catalyst is obtained through exchange modification; the addition amount of the compound is 2-10% of the mass of the kaolin. After the compound is added, the compound is removed later, and the environmental impact is caused. CN201210026633.0 and CN201110272476.7 are prepared by adding auxiliary agent polydimethyldiallyl ammonium chloride in the spray beating stage, crystallizing and modifying to obtain the catalyst, the adding amount of polydimethyldiallyl ammonium chloride is 1-10% of the mass of kaolin, the subsequent modification process is usually carried out for removing the organic matters by high-temperature roasting, so that the secondary pollution problem of the environment is caused, and the subsequent modification process is complex. The CN01142881.3 is prepared by adding components such as kaolin, solid seed crystal, auxiliary agent, organic dispersing agent, binder and the like in the preparation process, so as to obtain crystallized microspheres with NaY zeolite content of 20-70% and zeolite silicon-aluminum ratio of 4.0-6.0, and then roasting and exchanging the crystallized microspheres to obtain the catalyst product with high activity. Wherein the solid seed crystal is NaY, REY, HY or USY zeolite, and the addition amount of the solid seed crystal is 1-5% of the kaolin (mass). The organic dispersant is sodium polyacrylate and polyacrylamide, and the addition amount of the organic dispersant is 0.3-1.2 percent (mass) of kaolin. The organic template agent for generating pore canal is polyvinylpyrrolidone or polyvinyl alcohol, which is added in the preparation process of CN20090093113. X, the pore canal structure is modulated, and the activity of the catalyst is improved. However, organic matters are harmful to human bodies and are not friendly to the environment. CN201310293756.5, CN201110312397.4 change in situ crystallization catalyst preparation raw materials, and the pore structure and acidity of the catalyst are modulated by changing the properties of the raw materials. However, the change of the raw material property is limited, and the process flow is complex, which is not beneficial to industrial implementation. CN201010101799.5 reports that the pH of the catalyst slurry is adjusted stepwise or by mixing with aqueous glass, sodium metaaluminate, magnesium hydroxide or with ammonia water to obtain a catalyst with excellent heavy metal resistance, which has a long preparation process and a great difficulty in control. The magnesium compound is introduced into the CN201710630370. X to modulate the acidity, but the magnesium compound easily causes the agglomeration of the catalyst and the remarkable change of the acidity, and the implementation difficulty in the in-situ crystallization of the catalyst is higher Large; CN201610540179.9 reports a method for improving catalyst activity by using a vanadium-contaminated catalyst, wherein the valence of vanadium is changed from V +5 Reduce to V +4 Or V +3 The catalyst acidity is modulated. Since vanadium is a poison to the catalyst, this process may on the one hand result in an impaired catalyst performance and on the other hand also has the problem of vanadium loss. CN201010580187.9 discloses a method which can control the operation condition and reaction speed of the catalyst, respectively, and the product distribution is obviously improved after being used in a catalytic cracking device. CN102950031A, CN201110253602.4 improves catalyst activity by improvement of equipment process. Cn97109778.X provides a novel chemical dry process for increasing catalyst activity utilizing carbonylation to remove metals detrimental to catalyst activity from residuum and/or heavy oil catalytic cracking catalysts. CN200410029976.8 describes a catalytic cracking micro-explosion activator, which comprises a high-performance surfactant, water and a catalyst activator, and is mixed with raw materials before a catalytic cracking riser nozzle, and the water-in-oil micro-emulsion with nanoscale dimensions is formed by the water contained in the raw materials and absorbed by the raw materials, and is contacted with a high-temperature catalyst to generate micro-explosion, so that the atomization effect is improved, hydrocarbon fragments with active hydrogen are generated, and activated elements are adsorbed on the catalyst, so that the activity of the catalyst is improved, and the pollution of the catalyst is reduced. The invention discloses a heavy oil catalytic cracking catalyst and a preparation method thereof, in particular to a matrix material which can improve the activity of the catalytic cracking catalyst and has a pore volume of 0.8-2 mLg -1 A specific surface area of 150 to 350m 2 g -1 The most probable pore diameter is 30-100 nm, and the ratio of B/L acid is 0.8-2.0. The matrix material has the characteristics of strong heavy oil conversion capability and high activity in catalytic cracking reaction by modulating acid distribution and higher pore volume. CN201610239842.1 adopts other acid to replace hydrochloric acid in the process of acidifying peptization, so as to avoid damage of hydrochloric acid gas to molecular sieve in the process of roasting catalyst, and improve catalyst activity.
Through the analysis of the patent, the activity of the catalytic cracking catalyst is improved at present mainly through the change of raw materials, the modulation of a pore structure, the modification of elements and the innovation of a post-modification process flow. The change of the pore canal structure mostly adopts an organic template agent, and causes secondary pollution to the environment while the process is complex to implement; although the post-modification adopts different elements to perform modification, the modification amount and the introduction mode of the alkaline metal and other elements need to be considered for the in-situ crystallization catalyst, and the process flow is more complex; the improvement of equipment and catalytic cracking device can obviously improve the activity of the device, but has the defects of large investment, high risk and the like.
Disclosure of Invention
The invention aims to provide a method for improving the activity of a catalytic cracking catalyst, which aims to solve the problems of poor distribution of active centers, incomplete pore structure and need to further improve the activity of the catalyst in the existing preparation method.
To achieve the above object, the present invention provides a method for improving the activity of a catalytic cracking catalyst, comprising the steps of:
(1) Mixing a magnesium source, a silicon source and an aluminum source, and aging to obtain a magnesium-silicon-aluminum material;
(2) Mixing and pulping the magnesia-silica-alumina material with kaolin, seed crystal, water, dispersing agent and/or reinforcing agent, spraying, roasting and in-situ crystallization to obtain a crystallized product;
(3) Introducing the crystallized product after roasting into a downstream bed isomorphous substitution reactor to be in countercurrent contact with silicon tetrachloride for isomorphous substitution reaction; and
(4) Acid exchange or rare earth ion exchange is performed before the isomorphous substitution reaction or after the isomorphous substitution reaction.
The method for improving the activity of the catalytic cracking catalyst disclosed by the invention is characterized in that the aging condition in the step (1) is aging treatment for 10-600 minutes at 50-120 ℃, the aging temperature is preferably 80-100 ℃, and the aging treatment time is preferably 30-400 minutes.
The method for improving the activity of the catalytic cracking catalyst comprises the following steps of (1), wherein the molar ratio of Si to Mg is 0.1-20:1, preferably 0.1-15:1, si: al (Al) 2 O 3 The molar ratio of (2) is 0.1-20: 1, preferably 0.1 to 18:1.
The invention relates to a method for improving the activity of a catalytic cracking catalyst, wherein a silicon source in the step (1) is one or more of sodium silicate, silica sol and white carbon black; the magnesium source is one or more of magnesium chloride, magnesium nitrate and magnesium sulfate, and the aluminum source is one or more of aluminum sulfate, pseudo-boehmite, sodium metaaluminate, aluminum oxalate and aluminum hydroxide.
The method for improving the activity of the catalytic cracking catalyst comprises the following steps of (2) mixing a silicon-magnesium-aluminum material with kaolin in a mass ratio of 0.1-30:100, mixing a dispersing agent with kaolin in a mass ratio of 1-20:100, preferably 1-15:100, and mixing a reinforcing agent with kaolin in a mass ratio of 1-20:100, preferably 2-8:100.
The method for improving the activity of the catalytic cracking catalyst, disclosed by the invention, comprises the step (2) of spraying to obtain microspheres with the particle size of 20-110 mu m.
The method for improving the activity of the catalytic cracking catalyst disclosed by the invention is characterized in that the roasting temperature in the step (2) is 600-1000 ℃, the roasting time is 1-3 h, and the crystallization condition is 85-95 ℃ for 16-36 h.
Specifically, when the microspheres are roasted in the step (2), the microspheres can be roasted at 600-1000 ℃ for 1-3 hours to obtain low-temperature roasted microspheres, or can be roasted at 600-850 ℃ for 1-3 hours to obtain high-temperature roasted microspheres, or can be a mixture of the low-temperature roasted microspheres and the high-temperature roasted microspheres. After crystallization, filtering to remove mother liquor, washing filter cake with deionized water until pH is below 10.5, and drying to obtain a crystallized product with good pore structure and wear resistance and containing 20-60% NaY molecular sieve.
The method for improving the activity of the catalytic cracking catalyst is characterized in that the dispersing agent is sodium silicate and/or sodium pyrophosphate, the reinforcing agent is silica sol and/or aluminum sol, and the adding sequence of the dispersing agent and the reinforcing agent is not limited, and the dispersing agent and the reinforcing agent can be added simultaneously or in batches.
The method for improving the activity of the catalytic cracking catalyst comprises the step (2), wherein the kaolin is one or more of soft kaolin, hard kaolin and coal gangue, the bit diameter is 1.5-3.0 mu m, the content of crystalline kaolinite is higher than 80%, the ferric oxide is lower than 1.7%, and the sum of sodium oxide and potassium oxide is lower than 0.5%.
The invention relates to a method for improving the activity of a catalytic cracking catalyst, wherein seed crystal is one or more of NaY, REY modified by NaY and/or USY and silica-alumina gel, and the mass ratio of the seed crystal to kaolin is 0.1-10:100.
The method for improving the activity of the catalytic cracking catalyst comprises the step (3) of roasting to obtain microspherical materials with burning loss within 3 percent and containing 5-60 percent of Y-type molecular sieve.
The method for improving the activity of the catalytic cracking catalyst comprises the following steps of (3), wherein the mass ratio of silicon tetrachloride to the material after the crystallization product is roasted is 0.01-0.7: 1, preferably the mass ratio is 0.05-0.4: 1.
The composition of the guiding agent in the present invention is not particularly limited, and a general guiding agent may be used, for example, the guiding agent is prepared according to the composition of the guiding agent in example 1 of CN1232862a, and the molar ratio of the guiding agent recommended in the present invention is as follows: (14-16) SiO 2 :(0.7～1.3)Al 2 O 3 :(14～16)Na 2 O:(300～330)H 2 O。
The method for improving the activity of the catalytic cracking catalyst comprises the step (2) of roasting in a pretreatment furnace, wherein the pretreatment furnace comprises a feeding section, a roasting section and a discharging section, the total length of the pretreatment furnace is 0.5-5 m, the inner diameter of the pretreatment furnace is 0.01-1 m, and the roasting temperature is 100-1000 ℃.
The method for improving the activity of the catalytic cracking catalyst comprises the steps of arranging a heating system and a ventilation system on the outer layer of the pretreatment furnace in a furnace tile jacket mode, arranging the ventilation system on the inner wall of the pretreatment furnace, and enabling the ventilation system to input dry gas, nitrogen or water vapor into the pretreatment furnace.
The method for improving the activity of the catalytic cracking catalyst comprises the steps that an included angle alpha between a feed section of the pretreatment furnace and a main body of the pretreatment furnace is larger than 10 degrees and smaller than 90 degrees, and an included angle beta between the main body of the pretreatment furnace and a horizontal position is larger than 10 degrees and smaller than 90 degrees.
The invention relates to a method for improving catalytic cracking catalyst activity, wherein a shaft rotating device is arranged at the top of a pretreatment furnace to control the rotation of a furnace body of the pretreatment furnace, and the rotation frequency is 10-80 Hz/min.
The invention relates to a method for improving catalytic cracking catalyst activity, wherein the downer isomorphous substitution reactor is divided into a buffer zone and a reaction zone from top to bottom, the top of the buffer zone is provided with a catalyst inlet, the upper part of the buffer zone is provided with an atomizer communicated with the catalyst inlet, the bottom of the reaction zone is provided with a nitrogen inlet carrying silicon tetrachloride, the upper part of the reaction zone is provided with a discharge port, and the inner diameter ratio of the buffer zone to the reaction zone is 1:1 to 4:1, wherein the heights of the buffer zone and the reaction zone are respectively and independently 0.2-1 meter.
The method for improving the activity of the catalytic cracking catalyst, disclosed by the invention, comprises the steps of enabling the inner diameter ratio of the buffer zone to the reaction zone to be 1:1-3:1; preferably, a heating sleeve or a heating belt is arranged on the outer wall of the downer isomorphous substitution reactor; preferably, the diameter of the cavity of the reaction zone is 0.05-0.5 m.
The invention relates to a method for improving catalytic cracking catalyst activity, wherein the atomizer is made of stainless steel and comprises a plurality of symmetrically distributed gas holes, the diameter of each gas hole is 80-200 um, and the gas pressure in the atomizer is 0.1-6 MPa.
In the method for improving the activity of the catalytic cracking catalyst, in the step (3), the isomorphous substitution reaction temperature is 200-900 ℃, preferably 300-600 ℃, the contact time of the material after the roasting of the crystallized product and the silicon tetrachloride gas is 0.1-60 min, the silicon tetrachloride is carried into the reactor by taking nitrogen as carrier gas, and the proportion of the silicon tetrachloride to the total carrier gas is as follows: 0.1 to 100 percent.
The method for improving the activity of the catalytic cracking catalyst comprises the steps that acid used in acid exchange is one or more of sulfuric acid, oxalic acid, hydrochloric acid, phosphoric acid and nitric acid, hydrochloric acid and/or nitric acid are preferred, rare earth used in rare earth exchange is one or more of rare earth chloride, rare earth nitrate, rare earth hydroxide, rare earth carbonate and rare earth sulfate, and rare earth chloride and/or rare earth nitrate are preferred.
The invention relates to a method for improving the activity of a catalytic cracking catalyst, wherein the prepared catalyst Na 2 O is not more than 0.4%, and the specific surface is 200-500 m 2 Per gram, pore volume of 0.40-0.55 mL/g, unit cell constant of
The invention discloses a preparation method for improving the activity of a catalytic cracking catalyst, which mainly takes kaolin as a raw material, deionized water, a dispersing agent and/or a reinforcing agent, a magnesia-silica alumina material and seed crystals are added, and in-situ crystallization products are obtained through mixing, pulping, spraying and hydrothermal crystallization. The introduced magnesia-silica-alumina material forms a cross-linked structure in the microsphere precursor, improves the pore structure and the specific surface of the microsphere precursor, changes the synthesis microenvironment, combines the seed crystal and crystallization synthesis conditions, thereby effectively improving the number of growth points of the molecular sieve and obviously improving the content of the molecular sieve; on the other hand, in the design of the reactor, through the design of the partition reducing reaction and the feeding atomizer, the flow speed of the catalyst can be changed, and the contact efficiency with silicon tetrachloride is improved, so that the uniformity of the reaction of materials and silicon tetrachloride is ensured, and the reaction efficiency is improved. Meanwhile, according to the characteristics of the microsphere particles of the catalytic cracking catalyst, a gas-solid phase reaction principle of a down bed mode is adopted, and a device suitable for isomorphous substitution reaction of the microsphere catalyst is designed. The reverse contact mode can effectively solve the problems of back mixing of the catalyst and uneven distribution of catalyst particles along the radial direction caused by the reverse gravity operation of the ascending riser, and can realize the ultra-short contact operation of materials and reactants due to the improvement of the flow rate of gas-solid two phases, and has even reaction, so the reaction effect has outstanding superiority. The method has the most important point that the construction of the microsphere precursor pore canal and the gas phase superstable reaction are organically fused, and the activity of the catalytic cracking catalyst is comprehensively improved from the aspects of construction of the microsphere precursor pore canal, improvement of the molecular sieve content and improvement of the retention rate of the post-modified molecular sieve. Compared with the conventional hydrothermal ultrastable technology, the catalyst prepared by the method has the advantages of more developed strong acid, high activity and more excellent performance.
The beneficial effects of the invention are as follows:
1. make up for the requirement that the mesoporous volume of the catalyst is not developed and the content of the molecular sieve needs to be further improved. The introduced magnesia-silica-alumina material forms a cross-linked structure in the microsphere precursor, improves the pore structure and the specific surface of the microsphere precursor, changes the synthesis microenvironment, combines the seed crystal and crystallization synthesis conditions, thereby effectively improving the number of growth points of the molecular sieve and obviously improving the content of the molecular sieve.
2. The isomorphous substitution reaction efficiency is improved. In the design of the reactor, the flow speed of the catalyst can be changed and the contact efficiency with silicon tetrachloride can be improved through the design of the partition reducing reaction and the feeding atomizer, so that the uniformity of the reaction of materials and silicon tetrachloride is ensured and the reaction efficiency is improved.
3. The materials are more fully contacted, and the reaction efficiency is high. According to the characteristics of catalytic cracking catalyst microsphere particles, a gas-solid phase reaction principle of a downward bed mode is adopted, materials downward flow along a gravity field, and SiCl is adopted 4 And reversely contacting with the materials from bottom to top under the action of carrier gas. The contact mode can effectively solve the problems of back mixing of the catalyst and uneven distribution of catalyst particles along the radial direction caused by the reverse gravity operation of the ascending riser, and can realize the short-circuit contact operation of materials and reactants due to the improvement of the flow rate of gas-solid phases, and the reaction is uniform, so that the reaction effect is outstanding, and the method is very suitable for the rapid processing reaction process of gas and solid phases.
4. The isomorphous substitution reaction has high quality. The crystallinity retention rate of the isomorphous substituted catalyst is high, and the acidity is strong, so that the activity is obviously improved.
Drawings
FIG. 1 is a schematic diagram of a downer isomorphous substitution reactor.
FIG. 2 is a schematic structural diagram of an apparatus for preparing a catalytic cracking catalyst by an ammonium-free method according to the present invention.
FIG. 3 shows the angles between the pretreatment sections and the pretreatment furnaces.
Fig. 4 is a schematic structural view of the pretreatment furnace.
FIG. 5 shows the gasoline yields of the catalysts obtained in example 5 and comparative example 4 according to the present invention at different aging times;
wherein:
1. the pretreatment furnace, 2, a down bed isomorphous substitution reactor, 3, an absorption tower, 4, an exchange, a filter and flash evaporation drying equipment;
11. a feeding section, 12, a roasting section, 13, a discharging section, 14, a shaft rotating device, 15, a heating system, 16 and a ventilation system,
21. buffer zone 22, reaction zone 23, catalyst inlet 24, atomizer 25, nitrogen inlet with silicon tetrachloride, 26, discharge port 27, heating jacket.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
Referring to fig. 1, the downer isomorphous substitution reactor 2 provided by the invention is divided into a buffer zone 21 and a reaction zone 22 from top to bottom, wherein a catalyst inlet 23 is arranged at the top of the buffer zone 21, an atomizer 24 communicated with the catalyst inlet 23 is arranged at the upper part of the buffer zone 21, a nitrogen inlet 25 carrying silicon tetrachloride is arranged at the bottom of the reaction zone 22, a discharge port 26 is arranged at the upper part of the reaction zone 22, and the inner diameter ratio of the buffer zone 21 to the reaction zone 22 is 1:1 to 4:1, the heights of the buffer zone 21 and the reaction zone 22 are respectively and independently 0.2-1 m, and the weight ratio of silicon tetrachloride to the catalyst in the reaction zone 22 is 0.01-0.5:1.
Also, referring to fig. 1, a heating jacket 27 is provided on the outer wall of the downer type isomorphous substitution reactor 2, and of course, in other embodiments, the heating jacket 27 may be replaced by other heating structures, such as a heating belt.
In some embodiments, the reaction zone 22 preferably has a cavity diameter of 0.05 to 0.5 meters in size, and a height of 0.2 to 1 meter in size.
In some embodiments, the inner diameter ratio of buffer zone 21 to reaction zone 22 is preferably 1:1 to 3:1.
In some embodiments, the atomizer 24 is made of stainless steel, and comprises a plurality of symmetrically distributed air holes, wherein the diameter of each air hole is 80-200 um, and the pressure of air in the atomizer 24 is 0.1-6 MPa.
Referring to fig. 2, the device for preparing a catalytic cracking catalyst by an ammonium-free method provided by the invention comprises:
a pretreatment furnace 1 for roasting or hydrothermally treating the catalyst to obtain a pretreated catalyst;
the downstream bed type isomorphous substitution reactor 2 is used for carrying out isomorphous substitution reaction on the pretreated catalyst to obtain a reacted catalyst;
the absorption tower 3 is used for blowing the reacted catalyst into the absorption tower from a feed opening, and then carrying out tail gas neutralization reaction to obtain a catalyst intermediate;
exchange, filter and flash drying equipment 4, including exchange filters, for exchange and filtration of catalyst intermediates; flash drying equipment is used for flashing and drying the catalyst intermediate.
And, referring to fig. 3, the pretreatment furnace 1 comprises a feeding section 11, a roasting section 12 and a discharging section 13, the total length of the pretreatment furnace 1 is 0.5-5 m, the inner diameter is 0.01-1 m, and the roasting temperature is 100-1000 ℃.
Further, referring to fig. 4, the pretreatment furnace 1 includes a heating system 15 and a ventilation system 16, the heating system 15 is provided on the outer layer of the pretreatment furnace 1 in a furnace tile jacket manner, the ventilation system 16 is provided on the inner wall of the pretreatment furnace 1, and the ventilation system 16 is capable of supplying dry gas, nitrogen gas or water vapor into the interior of the pretreatment furnace 1.
And, referring to fig. 3, the angle α between the feed section 11 of the pretreatment furnace 1 and the main body of the pretreatment furnace 1 is greater than 10 ° and less than 90 °; referring to fig. 4, the included angle beta between the main body of the pretreatment furnace 1 and the horizontal position is more than 10 degrees and less than 90 degrees. The top of the pretreatment furnace 1 is provided with a shaft rotating device 14, the furnace body can rotate, the overturning of materials is realized through rotation, and the rotating frequency is 10-80 Hz/min.
The raw material sources are as follows:
1) Kaolin: industrial products, obtained from catalyst factories of Lanzhou petrochemical company
2) Magnesium chloride, chemical purity, national medicine group chemical reagent Co., ltd
3) Aluminum sulfate: industrial products, obtained from catalyst factories of Lanzhou petrochemical company
4) Sodium silicate solution: industrial products, obtained from catalyst factories of Lanzhou petrochemical company, (SiO) 2 :19.75％，Na 2 O：6.95％，H 2 O:73.30％)
5) Alkaline silica sol: industrial products, jitai Hengxin chemical engineering Co., ltd. (SiO 2: 30%)
6) High alkali sodium metaaluminate: industrial products, obtained from catalyst factories of Lanzhou petrochemical company
7) Guiding agent: industrial agents, taken from catalyst factories of Lanzhou petrochemical company, the ratio: 16SiO 2 :0.8Al 2 O 3 :15.7Na 2 O:312H 2 O
8) NaOH solution: industrial products, obtained from catalyst works of Lanzhou petrochemical Co (NaOH: 24%)
9) Sodium pyrophosphate: analytically pure, tianjin, denko chemical industries, ltd
10 Aluminum sol): industrial products, obtained from catalyst factories of Lanzhou petrochemical company (Al 2 O 3 :21.22％)
11 Seed crystal): industrial products, obtained from catalyst factories of Lanzhou petrochemical company
12 Hydrochloric acid): chemical purity
13 Nitric acid): chemical purity
14 Rare earth): chemical purity
The specific analysis method comprises the following steps:
crystallinity of NaY molecular sieves the crystallinity of the samples was measured by X-ray diffraction method on a D/max-3C X-ray powder diffractometer manufactured by Rigaku corporation, japan, and the method standard was Q/SYLS 0596-2002. The test of the Si/Al ratio of the NaY molecular sieve adopts an X-ray powder diffraction method, and the method standard is Q/SYLS 0573-2002. Sample pore distribution test the specific surface area, pore size distribution and pore volume of the sample were determined by an N2 low temperature (77.3K) adsorption-desorption experimental method using an Autosorb-3B specific surface determinator from Quantachrome company, america. Microreaction Activity (MA) evaluation: the method of ASTM-D3907 is adopted, the catalyst is treated for 17 hours under the conditions of 800 ℃ and 100% water vapor in advance, the light diesel oil in large harbor is used as reaction raw oil, the reaction temperature is 460 ℃, the oil inlet time is 70 seconds, the catalyst loading amount is 2.5-5 g, and the yield of the gasoline after the reaction is analyzed by GC 7890. IR acidity characterization was performed on a bruker TENSOR27 type infrared spectrum. Reaction performance evaluation: the selectivity of the catalytic cracking reaction was evaluated in the us ACE catalytic cracking unit. The catalyst was previously treated at 800℃with 100% steam for 17 hours. The reaction temperature is 510-540 ℃, and the catalyst-oil ratio is 4-10.
Example 1
10g of magnesium chloride was dissolved in 80mL of distilled water, the dissolved solution and 8.16g of pseudo-boehmite were slowly poured into 242mL of sodium silicate solution, si/mg=9.6 (molar ratio), si/Al 2 O 3 =20 (molar ratio), mixing for 30 minutes, final pH 9.2, aging at 50 ℃ for 600 minutes, preparing mixed slurry with solid content of 46% from 100g of aged material, 6667g (burning base) of kaolin, 666.7g of nay666.7g of sodium silicate solution 333.35g of alkaline silica sol 1333.4g of deionized water, and spray drying to obtain 5300g of spray microsphere P1 with particle size of 20-110 μm. Roasting one part of the P1 spray soil ball for 2.7 hours at 925 ℃ to obtain a roasted microsphere G1, roasting the other part of the P1 spray soil ball for 2.5 hours at 650 ℃ to obtain a roasted microsphere B1, mixing 200G of G1 with 300G of B1, adding a sodium silicate solution, a guiding agent, a sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization for 30 hours at 95 ℃, filtering to remove mother liquor, washing with water, and drying to obtain a product J1.
1 was baked in a pretreatment furnace at 600℃for 2 hours with 70% steam to obtain a baked material having a burning loss of 1.6%. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 200 mu m and the pressure of 6MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 100% of carrier gas, the gas-solid phase reaction temperature is 390 ℃, the contact time with the gas is 30min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to an in-situ crystallization catalyst is 0.02:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.3 meter and 0.7 meter respectively. The reacted materials are purged for 60min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 15% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. After the catalyst is collected by a collector at the bottom of the absorption tower,
Washing with 16 times of water at 75deg.C for 1 hr, treating the obtained product with nitric acid, nitric acid/product=0.07, exchanging at pH=3.0-4.5 and 93 deg.C for 1.5 hr, filtering to remove filtrate, and drying filter cake to obtain Na 2 Catalyst C-1 with O content of 0.46%.
Example 2
150g of magnesium nitrate was dissolved in 320mL of distilled water, the dissolved solution was slowly poured into 101g of an alkaline silica sol solution, mixed for 50 minutes, 9.15 g of pseudo-boehmite was added, the final pH was 8.1, si/mg=0.5 (molar ratio), si/Al 2 O 3 The mixed material was aged at 120 ℃ for 10min, 100g of the aged material, 671g (burning group) of kaolin, 40.26g of REY, 46.97g of sodium pyrophosphate, 6.71g of aluminum sol and deionized water were prepared into a mixed slurry with a solid content of 32%, and spray-dried to obtain 300g of spray microspheres P2 with a particle size of 20-110 μm. And roasting the P2 spray soil ball at 990 ℃ for 1.5h to obtain a roasted microsphere G2. 100g of G2 is added into sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, and is subjected to hydrothermal crystallization at 85 ℃ for 16 hours, mother liquor is removed by filtration, and the product J2 is obtained by washing and drying.
2, carrying out rare earth hydroxide exchange on J2, wherein cerium hydroxide/crystallization product=0.14, exchanging for 1 hour at the pH value=3.3-3.9 and 90 ℃, filtering to remove filtrate, washing a filter cake by deionized water, and roasting for 2 hours at the temperature of 550 ℃ in a pretreatment furnace and the water vapor content of 65%, thereby obtaining a roasting material with the burning loss of 1.9%. The roasting material is slowly added into the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 50 mu m and the pressure of 0.11MPa, catalyst particles are dispersed in the reactor through the spraying of the atomizer, and the catalyst particles run downwards and meet with silicon tetrachloride gas, wherein the silicon tetrachloride accounts for 10% of carrier gas, the gas-solid phase reaction temperature is 310 ℃, and the contact time with the gas is 30 min, controlling the flow of gas, and ensuring that the ratio of silicon tetrachloride to the in-situ crystallization catalyst is 0.33:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.3 meter and 0.7 meter respectively. The reacted materials are purged for 60min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 15% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. Collecting the catalyst by a collector at the bottom of the absorption tower, washing with 10 times of water at 95 ℃ for 1h, and drying to obtain Na 2 Catalyst C-2 with O content of 0.36%.
Example 3
50g of magnesium sulfate was dissolved in 220mL of distilled water, 229g of white carbon black was dissolved in 500mL of distilled water to form a turbid solution, a magnesium sulfate solution and 534mL of aluminum sulfate solution were slowly poured into the white carbon black solution, and mixed for 60 minutes, the final pH value was 8.0, si/Mg=8.7 (molar ratio), si/Al 2 O 3 The mixed material was aged at 70 ℃ for 200min with the molar ratio of 7.7, 300g of the aged material, 1322g of kaolin (burning group), 13.22g of REHY, 198.3g of sodium silicate solution, 198.3g of alumina sol and deionized water were prepared into a mixed slurry with a solid content of 40%, and spray-dried to obtain 600g of spray soil balls P3 with a particle size of 20-110 μm. And roasting the P3 spray soil ball at 990 ℃ for 1.5h to obtain a roasted microsphere G3. 100g of G3 is added with sodium silicate, a guiding agent, sodium hydroxide solution and deionized water, and is subjected to hydrothermal crystallization at 85 ℃ for 16 hours, the mother solution is removed by filtration, and the product J3 is obtained by washing and drying.
J3 was exchanged with phosphoric acid and lanthanum nitrate, the phosphoric acid/crystallized product=0.05 (mass ratio), lanthanum nitrate (calculated as lanthanum oxide)/crystallized product=0.03, and the mixture was exchanged at ph=4.0 to 4.5 and 93 ℃ for 1.5 hours, the filtrate was removed by filtration, and the cake was calcined at 660 ℃ in a pretreatment furnace for 1.5 hours with 40% steam to obtain a calcined material having a burning loss of 2.1%. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 140 mu m and the pressure of 3MPa, catalyst particles are dispersed in the reactor through the spraying of the atomizer, the catalyst particles run downwards and meet with silicon tetrachloride gas, the silicon tetrachloride accounts for 30% of carrier gas, and the gas phase and the solid phase are reversedThe temperature is 470 ℃, the contact time with the gas is 45min, the flow rate of the gas is controlled, and the ratio of silicon tetrachloride to the in-situ crystallization catalyst is 0.24:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.3 meter and 0.7 meter respectively. The reacted materials are purged for 60min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 15% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. Collecting the catalyst by an absorber bottom collector, washing with 8 times of water at 95 ℃ for 2 hours, washing with deionized water, and drying to obtain Na 2 Catalyst C-3 with O content of 0.38%.
Example 4
13.61g of magnesium carbonate was dissolved in 260mL of distilled water, the dissolved magnesium carbonate solution was slowly added to 648g of an alkaline silica sol, 278 g of pseudo-boehmite was added, and the mixture was mixed for 60 minutes, with a final pH of 10.3, si/Mg=20 (molar ratio), si/Al 2 O 3 The mixed material is aged at 100 ℃ for 60min, 200g of aged material, 1282g of kaolin (burning base), naY38.46g, 243.58g of sodium pyrophosphate, 205.12g of alkaline silica sol and deionized water are prepared into mixed slurry with the solid content of 47%, and spray drying is carried out to obtain 1100g of spray microsphere P4 with the particle size of 20-110 mu m. And (3) roasting one part of P4 at 1000 ℃ for 1.5 hours to obtain roasted microspheres G4, roasting the other part of P4 at 800 ℃ for 2 hours to obtain roasted microspheres B4, adding 800G G4 and 200G B4 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization at 89 ℃ for 30 hours, filtering to remove mother liquor, washing with water, and drying to obtain a product J4.
The J4 is roasted for 1.5 hours in a pretreatment furnace 680 ℃ and the water vapor amount is 20%, and a roasting material with the burning loss of 2.5% is obtained. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 145 mu m and the pressure of 3MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 50% of carrier gas, the gas-solid phase reaction temperature is 380 ℃, the contact time with the gas is 60min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to an in-situ crystallization catalyst is 0.08:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.3 meter and 0.7 meter respectively. The reacted materials are purged for 60min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 15% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. After the catalyst is collected by a collector at the bottom of the absorption tower,
Washing the materials for 2 hours at 85 ℃ with 13 times of water, then exchanging with hydrochloric acid and rare earth chloride, wherein the hydrochloric acid/product is 0.10, the cerium chloride (calculated as cerium oxide)/product is 0.15, exchanging for 1.5 hours at 93 ℃ with pH value of 4.0-4.5, filtering to remove filtrate, washing the filter cake with deionized water, and drying to obtain Na 2 Catalyst C-4 with O content of 0.43%.
Example 5
30g of magnesium nitrate is dissolved by 160mL of distilled water, 83g of white carbon black is gradually dissolved in 200mL of distilled water to form a turbid solution, the dissolved magnesium nitrate solution and 42.6 g of pseudo-boehmite are slowly added into the turbid solution of white carbon black, and the mixture is mixed for 30 minutes, wherein the final pH value is 9.3, si/Mg=6.5 (molar ratio), si/Al 2 O 3 The mixed material was aged at 90 ℃ for 240min, 50g of the aged material, 575g of kaolin (burning group), 28.75g of REY, 74.75g of sodium silicate solution, 74.75g of alkaline silica sol and deionized water were prepared into a mixed slurry with a solid content of 43%, and spray-dried to obtain 500g of spray microspheres P5 with a particle size of 20-110 μm. Roasting one part of P5 at 970 ℃ for 2.3 hours to obtain roasted microsphere G5, roasting the other part of P5 at 850 ℃ for 1.9 hours to obtain roasted microsphere B5, adding 200G of G5 and 200G of B5 into sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, performing hydrothermal crystallization at 87 ℃ for 16 hours, filtering to remove mother liquor, washing with water and drying to obtain a product J5.
And (3) roasting J5 for 0.5 hour at 800 ℃ in a pretreatment furnace and 90% of water vapor to obtain a roasted material with the burning loss of 2.2%. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 180 mu m and the pressure of 5MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 80% of carrier gas, the gas-solid phase reaction temperature is 400 ℃, the contact time with the gas is 30min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to an in-situ crystallization catalyst is 0.16:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.3 meter and 0.7 meter respectively. The reacted materials are purged for 60min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 15% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. After the catalyst is collected by a collector at the bottom of the absorption tower,
washing the materials for 0.6h at 85 ℃ with 5 times of water, and then exchanging with rare earth nitrate under the following exchange conditions: lanthanum nitrate (calculated as lanthanum oxide)/crystallized product=0.07, pH=4.2, temperature 70 ℃, treatment time 1h, filtrate removal of exchanged materials, washing filter cake with deionized water, drying to obtain Na 2 Catalyst C-5 with O content of 0.38%.
Example 6
100g of magnesium sulfate was dissolved in 500mL of distilled water, the dissolved solution was slowly added to 675mL of sodium silicate solution, mixed for 70 minutes, the final pH was 12.3, 664mL of aluminum sulfate, si/mg=2.7 (molar ratio), si/Al was added 2 O 3 The mixed material is aged for 180min at 80 ℃, 200g of aged material, 7143g (burning base) of kaolin, USY642.87g, 642.87g of sodium pyrophosphate, 642.87g of alkaline silica sol and deionized water are prepared into mixed slurry with the solid content of 38%, and spray drying is carried out to obtain 3500g of spray microsphere P6 with the particle size of 20-110 mu m. Roasting one part of P6 at 960 ℃ for 1.4 hours to obtain roasted microsphere G6, roasting the other part of P6 at 880 ℃ for 2 hours to obtain roasted microsphere B6, adding 600G of G6 and 400G of B6 into sodium silicate, a guiding agent, a sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization at 92 ℃ for 34 hours, filtering to remove mother liquor, washing with water and drying to obtain a product J6.
J6 is roasted for 2 hours in a pretreatment furnace at 750 ℃ and with the water vapor amount of 30%, and a roasted material with the burning loss of 1.9% is obtained. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 140 mu m and the pressure of 3MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 90% of carrier gas, the gas-solid phase reaction temperature is 450 ℃, the contact time with the gas is 15min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to an in-situ crystallization catalyst is 0.34:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.3 meter and 0.7 meter respectively. The reacted materials are purged for 60min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 15% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. After the catalyst is collected by a collector at the bottom of the absorption tower,
Washing with 8 times of water at 75deg.C for 1.5 hr, reacting with rare earth chloride, yttrium chloride (calculated as yttrium oxide)/product=0.10 (mass ratio), exchanging for 30min at pH=3.5-4.0 and 95deg.C, filtering to remove filtrate, washing filter cake with deionized water, and drying to obtain Na 2 Catalyst C-6 with O content of 0.42%.
Example 7
16.88g of magnesium chloride is dissolved in 300mL of distilled water, the dissolved solution is slowly added into 604g of alkaline silica sol solution, mixed for 55 minutes, the final pH value is 11.5, 372mL of aluminum sulfate, si/Mg=17 (molar ratio) and Si/Al are added 2 O 3 The mixed material was aged at 110 ℃ for 120min, 300g of the aged material, 2273g (burning base) of kaolin, 90.92g of REHY, 45.46g of sodium silicate solution, 68.19g of alumina sol and deionized water were prepared into a mixed slurry with a solid content of 36%, and spray-dried to obtain 5500g of spray microspheres P7 with a particle size of 20-110 μm. Roasting one part of P7 at 850 ℃ for 2.3 hours to obtain roasted microspheres G7, roasting the other part of P7 at 680 ℃ for 2.6 hours to obtain roasted microspheres B7, adding 750G of G7 and 250G of B7 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization at 92 ℃ for 32 hours, filtering to remove mother liquor, washing with water, and drying to obtain a product J7.
Exchange J7 with sulfuric acid, sulfuric acid/crystallized product=0.20 (mass ratio), ph=3.5 to 4Exchanging for 45min at 0 and 65 ℃, filtering to remove filtrate, washing a filter cake with deionized water, and roasting the filter cake for 0.5 hour at 850 ℃ in a pretreatment furnace with water vapor content of 60%, thereby obtaining a roasting material with the burning loss of 2.4%. 500 g of roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 70 mu m and the pressure of 3.5MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 60% of carrier gas, the gas-solid phase reaction temperature is 520 ℃, the gas contact time is 10min, the flow rate of the gas is controlled, and the ratio of silicon tetrachloride to in-situ crystallization catalyst is 0.28:1. the inner diameters of the buffer zone and the reaction zone are: 0.25 m, and heights of 0.6 m and 0.9 m, respectively. After the reacted materials are purged for 20min through an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 13% sodium hydroxide solution, and acid-base neutralization and collection are carried out on the reacted gas. Washing the reacted material with 2 times of water at 35 ℃ for 2 hours, and drying to obtain Na 2 Catalyst C-7 with O content of 0.49%.
Example 8
130g of magnesium nitrate are dissolved in 400mL of distilled water, the dissolved solution is slowly added into 947mL of sodium silicate solution, mixed for 25 minutes, the final pH value is 10.5, 41.75 g of pseudo-boehmite is added, si/Mg=5.4 (molar ratio), si/Al is added 2 O 3 The mixed material was aged at 105 ℃ for 300min, 200g of the aged material, 4167g (burning base), REY291.69g, 333.36g of sodium silicate solution, 291.69g of alumina sol and deionized water were prepared into a mixed slurry with a solid content of 42%, and spray drying was performed to obtain 750g of spray microspheres P8 with a particle size of 20-110 μm. Roasting P8 at 630 ℃ for 2.1h to obtain roasted microspheres B8, adding 600g of B8 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, performing hydrothermal crystallization at 94 ℃ for 36h, filtering to remove mother liquor, washing with water, and drying to obtain a product J8.
Exchanging J8 with rare earth nitrate, namely lanthanum nitrate (calculated by lanthanum oxide)/crystallized product=0.15 (mass ratio), exchanging for 60min at the condition of pH=3.0-3.5 and 85 ℃, and pre-treatingRoasting for 2 hours at 600 ℃ with the water vapor content of 70% to obtain a roasted material with the burning loss of 2.2%. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 85 mu m and the pressure of 4.7MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 20% of carrier gas, the gas-solid phase reaction temperature is 600 ℃, the contact time with the gas is 2min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to the in-situ crystallization catalyst is 0.42:1. the inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.8 meter and 1 meter respectively. The reacted material is purged for 50min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 10% sodium carbonate solution, the reacted gas is neutralized and collected by acid and alkali, the reacted material is washed for 1h by 15 times of water at 65 ℃, the filtrate is removed by filtering the product, and the filter cake is washed by deionized water and dried to obtain Na 2 Catalyst C-8 with O content of 0.39%.
Example 9
200g of magnesium nitrate is dissolved by 700mL of distilled water, 1173g of white carbon black is gradually dissolved in 1000mL of distilled water to form a turbid solution, the dissolved magnesium nitrate solution is slowly added into the turbid solution of the white carbon black, 3157 g of pseudo-boehmite is added, and the mixture is mixed for 90 minutes, wherein the final pH value is 7.3, si/Mg=7.8 (molar ratio), si/Al 2 O 3 The mixed material is aged for 400min at 95 ℃ with the molar ratio of 0.6, 500g of aged material, 2841g (burning base) of kaolin, 227.28g of REHY, 426.15g of sodium pyrophosphate, 511.38g of alkaline silica sol and deionized water are prepared into mixed slurry with the solid content of 42%, and the mixed slurry is spray-dried to obtain 1550g of spray microspheres P9 with the particle size of 20-110 mu m.
Roasting one part of P9 at 890 ℃ for 1.5 hours to obtain roasted microspheres G9, roasting the other part of P9 at 770 ℃ for 1.8 hours to obtain roasted microspheres B9, adding 200G of G9 and 400G of B9 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization at 88 ℃ for 28 hours, filtering to remove mother liquor, washing with water, and drying to obtain a product J9.
With J9 atRoasting for 0.5 hours at 600 ℃ in a pretreatment furnace and 20% of water vapor to obtain a roasted material with 1.8% burning loss. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 160 mu m and the pressure of 5.5MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 40% of carrier gas, the gas-solid phase reaction temperature is 350 ℃, the contact time with the gas is 1min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to the in-situ crystallization catalyst is 0.36:1. The inner diameters of the buffer zone and the reaction zone are: 0.5 m, and heights of 0.9 m and 0.4 m respectively. After the reacted materials are purged for 35min through an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 8% sodium carbonate solution, and the reacted gas is subjected to acid-base neutralization and collection. After the catalyst is collected by a collector at the bottom of the absorption tower, the material is washed for 1h by 5 times of water at 95 ℃, the washed material is exchanged by sulfuric acid, sulfuric acid/product=0.13 (mass ratio), the material is exchanged for 60min under the conditions of pH=3.0-3.5 and 85 ℃, the filtrate is removed by filtration, and the filter cake is washed by deionized water and dried to obtain Na 2 Catalyst C-9 with O content of 0.35%.
Example 10
9g of magnesium chloride is dissolved by 200mL of distilled water, the dissolved solution is slowly added into 246g of alkaline silica sol solution, mixed for 70 minutes, the final pH value is 8.5, 16.06 g of pseudo-boehmite is added, si/Mg=13 (molar ratio) is added, and Si/Al is added 2 O 3 The mixed material was aged at 60 ℃ for 500min, 200g of the aged material, 787.4g (burning base) of kaolin, 15.75g of nay, 86.61g of sodium pyrophosphate, 118.11g of alkaline silica sol and deionized water were prepared into a mixed slurry with a solid content of 36%, and spray-dried to obtain 2100g of spray microspheres P10 with a particle size of 20-110 μm. Roasting one part of P10 at 830 ℃ for 2.8 hours to obtain roasted microsphere G10, roasting the other part of P10 at 670 ℃ for 3.6 hours to obtain roasted microsphere B10, adding 900G of G10 and 300G of B10 into sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, performing hydrothermal crystallization at 92 ℃ for 32 hours, filtering to remove mother liquor, washing with water and drying to obtain a product J10.
J10 was baked in a pretreatment furnace at 560℃for 2 hours with 30% of water vapor to obtain a baked material having a burning loss of 1.9%. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 140 mu m and the pressure of 3MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 50% of carrier gas, the gas-solid phase reaction temperature is 330 ℃, the contact time with the gas is 30min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to an in-situ crystallization catalyst is 0.49:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.3 meter and 0.7 meter respectively. The reacted materials are purged for 60min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 15% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. After the catalyst is collected by a collector at the bottom of the absorption tower,
Washing the materials with 19 times of water at 85 ℃ for 0.5h, exchanging the products with hydrochloric acid, exchanging hydrochloric acid/crystallized product with the ratio of hydrochloric acid/crystallized product being 0.2 (mass ratio) for 40min at the condition of pH value of 3.0-3.5 and 90 ℃, filtering to remove filtrate, washing the filter cake with deionized water, and drying to obtain Na 2 Catalyst C-10 with O content of 0.44%.
Comparative example 1
In contrast to example 3, 229g of white carbon black was dissolved in 500ml of distilled water to form a cloudy solution, which was aged at 70℃for 200 minutes, and 300g of the aged material, 885g of kaolin (burning base), REHY8.85g, 132.75g of sodium silicate solution, 44.25g of alumina sol and deionized water were prepared to prepare a mixed slurry having a solid content of 40%, and spray-dried to obtain 600g of spray soil balls P11 having a particle size of 20 to 110. Mu.m. And roasting the P11 spray soil ball at 990 ℃ for 1.5h to obtain a roasted microsphere G11. 100g of G11 is added with sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, and is subjected to hydrothermal crystallization at 85 ℃ for 16 hours, mother liquor is removed by filtration, and the product J11 is obtained by washing and drying.
Exchange J11 with phosphoric acid, rare earth nitrate, phosphoric acid/crystallized product=0.05 (mass ratio), lanthanum nitrate (calculated as lanthanum oxide)/crystallized productSubstance=0.03 (mass ratio), exchange for 1.5 hours at ph=4.0 to 4.5 and 93 ℃, filter to remove filtrate, and bake the filter cake for 1.5 hours at 660 ℃ and 40% water vapor to obtain a baked material with a burning loss of 2.1%. The roasting material is slowly added to the top end of the reactor through a feeder and reacts with silicon tetrachloride gas in the same direction, silicon tetrachloride accounts for 30% of carrier gas, the gas-solid phase reaction temperature is 470 ℃, the contact time with the gas is 45min, the flow of the gas is controlled, and the ratio of silicon tetrachloride to in-situ crystallization catalyst is 0.24:1. And (5) neutralizing the reacted gas with acid and alkali, and collecting. Washing the catalyst with 8 times of water at 95 ℃ for 2 hours, washing with deionized water, and drying to obtain Na 2 Catalyst C-11 with O content of 0.39%.
Comparative example 2
In contrast to example 1, 10g of magnesium chloride was dissolved in 80mL of distilled water, aged at 50℃for 600 minutes, and 10g of the aged material, 666.7g (burning base) of kaolin, 33.34g of sodium silicate solution, 133.34g of alkaline silica sol and deionized water were prepared to prepare a mixed slurry having a solid content of 46%, and spray-dried to obtain 530g of spray microspheres P12 having a particle size of 20 to 110. Mu.m. Roasting one part of the P12 spray soil ball for 2.7 hours at 925 ℃ to obtain roasted microspheres G12, roasting the other part of the P12 spray soil ball for 2.5 hours at 650 ℃ to obtain roasted microspheres B12, mixing 200G of G12 with 300G of B12, adding sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization for 30 hours at 95 ℃, filtering to remove mother liquor, washing with water, and drying to obtain a product J12.
And (3) roasting J12 for 2 hours at 600 ℃ in a roasting furnace and 70% of water vapor to obtain a roasted material with the burning loss of 1.6%. The roasting material and silicon tetrachloride flow into the inclined reactor in the same direction slowly, the proportion of silicon tetrachloride to carrier gas is 100%, the gas-solid phase reaction temperature is 390 ℃, the contact time with the gas is 30min, and the proportion of silicon tetrachloride to in-situ crystallization catalyst is 0.02:1. Neutralizing the gas after reaction with 15% sodium hydroxide solution, washing the catalyst with 16 times of water at 75 ℃ for 1h, treating the obtained product with nitric acid, exchanging nitric acid/product=0.07 at pH=3.0-4.5 and 93 ℃ for 1.5 h, filtering to remove filtrate, and drying the filter cake to obtain Na 2 Catalyst C-12 with O content of 0.46%.
Comparative example 3
In contrast to example 7, 16.88g of magnesium chloride was dissolved in 300mL of distilled water, the dissolved solution was slowly added to 604g of an alkaline silica sol solution, mixed for 55 minutes, the final pH was 11.5, si/mg=17 (molar ratio), the mixed material was aged at 110 ℃ for 120 minutes, 300g of the aged material, 2273g (glowing group) of kaolin, 45.46g of a sodium silicate solution, 68.19g of alumina sol, deionized water were prepared as a mixed slurry having a solid content of 36%, and spray-dried to obtain 5500g of spray microspheres P13 having a particle size of 20 to 110 μm. Roasting one part of P13 at 850 ℃ for 2.3 hours to obtain roasted microspheres G13, roasting the other part of P13 at 680 ℃ for 2.6 hours to obtain roasted microspheres B13, adding 750G of G13 and 250G of B13 into sodium silicate, a guiding agent, a sodium hydroxide solution and deionized water, performing hydrothermal crystallization at 92 ℃ for 32 hours, filtering to remove mother liquor, washing with water, and drying to obtain a product J13.
And (3) exchanging J13 with sulfuric acid, wherein the sulfuric acid/crystallized product=0.20 (mass ratio), exchanging for 45min at the pH value=3.5-4.0 and the temperature of 65 ℃, filtering to remove filtrate, washing a filter cake with deionized water, and roasting the filter cake for 0.5 hour at the temperature of 850 ℃ in a roasting furnace and the water vapor amount of 60%, thereby obtaining a roasting material with the burning loss of 2.4%. The roasting material and silicon tetrachloride are added from the top end of the reactor in the same direction, the proportion of silicon tetrachloride to carrier gas is 60 percent, the gas-solid phase reaction temperature is 520 ℃, the contact time with the gas is 10 minutes, and the proportion of silicon tetrachloride to the roasting material is 0.28:1. the gas after the reaction was neutralized with 13% sodium hydroxide solution. Washing the reacted material with 2 times of water at 35 ℃ for 2 hours, and drying to obtain Na 2 Catalyst C-13 having an O content of 0.49%.
Comparative example 4
In contrast to example 5, 30g of magnesium nitrate was dissolved with 160mL of distilled water, 83g of white carbon black was gradually dissolved in 200mL of distilled water to form a turbid solution, the dissolved magnesium nitrate solution was slowly added to the turbid solution of white carbon black, mixed for 30 minutes, the final pH was 9.3, si/mg=6.5 (molar ratio), the mixed material was aged at 90 ℃ for 240 minutes, 50g of the aged material, 575g of kaolin (burn base), rey28.75g of sodium silicate solution 74.75g of alkaline silica sol 74.75g of deionized water was prepared as a mixed slurry having a solid content of 43%, and spray-dried to obtain 500g of spray microspheres P14 having a particle size of 20 to 110 μm. Roasting one part of P14 at 970 ℃ for 2.3 hours to obtain roasted microsphere G14, roasting the other part of P14 at 850 ℃ for 1.9 hours to obtain roasted microsphere B14, adding 200G of G14 and 200G of B14 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, performing hydrothermal crystallization at 87 ℃ for 16 hours, filtering to remove mother liquor, washing with water and drying to obtain a product J14.
Adding the crystallized product prepared in the comparative example 44, ammonium sulfate, ammonium chloride and deionized water into a stainless steel kettle under stirring, wherein the ammonium sulfate/crystallized product=0.30 (mass ratio), the ammonium chloride/crystallized product=0.10 (mass ratio), exchanging for 1 hour at the conditions of pH=3.0-3.5 and 90 ℃, filtering to remove filtrate, washing a filter cake with deionized water, and drying to obtain a mixed material; roasting the mixture at 500 ℃ for 2 hours under the condition that the water vapor inlet amount is 85 percent to obtain a roasted material; the baked material is exchanged once by rare earth nitrate, and the exchange conditions are as follows: lanthanum nitrate (calculated by lanthanum oxide)/one baked material=0.07, pH=4.2, the temperature is 70 ℃, the time is 1 hour, and the exchanged materials are filtered, washed and dried to obtain two mixed materials; roasting the secondary mixed material for 1.5 hours at 600 ℃ under the condition that the water vapor inlet amount is 80 percent to obtain a secondary roasted material; exchanging the secondary roasting material with ammonium chloride, wherein the ammonium chloride/secondary roasting material is 0.45 and the pH value is 3.8-4.5, filtering, washing and drying the exchanged product to obtain Na 2 Catalyst cat-14 with O content of 0.35%.
The crystallization conditions and crystallization results of examples 1 to 10 and comparative examples 1 to 4 are shown in Table 1, the pore structure test results of the crystallized products are shown in Table 2, and the pore structure results of Table 2 indicate that: the synthetic method of the patent can prepare a crystallized product with a developed pore structure. The addition of the Si-Mg-Al structural material brings about the change of the microsphere precursor structure in the synthesis system, thereby improving the pore structure of the crystallized product. Compared with the material which simply uses silicon or magnesium or aluminum, the crystallization product prepared by the scheme has more abundant pore structure. The catalyst acidity results of table 3 show: the strong B acid amount of the catalyst subjected to isomorphous substitution is obviously increased, and the total B acid amount is obviously increased, which is beneficial to improving the activity of the catalyst and enhancing the primary cracking performance. Table 4 catalyst evaluation results show: the catalyst with more developed pore structure and higher activity shows better heavy oil conversion and gasoline yield and coke selectivity.
The results of fig. 5 show that the in-situ crystallization catalyst prepared by the technical scheme provided by the patent has higher gasoline yield under different aging time due to high activity.
TABLE 1 in situ crystallization process conditions and preparation results
TABLE 2 pore structure characteristics of crystallized products
Table 3 characterization of catalyst acidity
Table 4 catalyst reactivity (ACE evaluation under 5000V, 3000Ni contamination conditions)
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (22)
1. A method for increasing the activity of a catalytic cracking catalyst comprising the steps of:
(1) Mixing a magnesium source, a silicon source and an aluminum source, and aging to obtain a magnesium-silicon-aluminum material;
(2) Mixing and pulping the magnesia-silica-alumina material with kaolin, seed crystal, water, dispersing agent and/or reinforcing agent, spraying, roasting and in-situ crystallization to obtain a crystallized product;
(3) Introducing the crystallized product after roasting into a downstream bed isomorphous substitution reactor to be in countercurrent contact with silicon tetrachloride for isomorphous substitution reaction; and
(4) Acid exchange and/or rare earth ion exchange is performed before or after the isomorphous substitution reaction.
2. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the aging condition in step (1) is aging at 50 to 120 ℃ for 10 to 600 minutes, preferably 80 to 100 ℃ and the aging time is preferably 30 to 400 minutes.
3. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the molar ratio of Si to Mg in step (1) is 0.1 to 20:1, preferably 0.1 to 15:1, si: al (Al) 2 O 3 The molar ratio of (2) is 0.1-20: 1, preferably 0.1 to 18:1.
4. the method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the silicon source in the step (1) is one or more of water glass, silica sol and white carbon black; the magnesium source is one or more of magnesium chloride, magnesium nitrate and magnesium sulfate, and the aluminum source is one or more of aluminum sulfate, pseudo-boehmite, sodium metaaluminate, aluminum oxalate and aluminum hydroxide.
5. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein in the step (2), the mass ratio of the silicon-magnesium-aluminum material to the kaolin is 0.1-30:100, the mass ratio of the dispersant to the kaolin is 1-20:100, preferably 1-15:100, and the mass ratio of the reinforcing agent to the kaolin is 1-20:100, preferably 2-8:100.
6. The method of improving the activity of a catalytic cracking catalyst according to claim, wherein the particles obtained by spraying in the step (2) have a particle size of 20 to 110. Mu.m.
7. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the calcination temperature in step (2) is 600 to 1000 ℃, the calcination time is 1 to 3 hours, and the crystallization conditions are 85 to 95 ℃ and 16 to 36 hours.
8. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the dispersing agent is sodium silicate and/or sodium pyrophosphate; the reinforcing agent is silica sol and/or aluminum sol.
9. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the kaolin in the step (2) is soft kaolin and/or hard kaolin, wherein the bit diameter is 1.5-3.0 μm, the content of crystalline kaolinite is higher than 80%, the iron oxide is lower than 1.7%, and the sum of sodium oxide and potassium oxide is lower than 0.5%.
10. The method for improving the activity of the catalytic cracking catalyst according to claim 1, wherein the seed crystal is one or more of NaY, naY modified REY and/or USY and silica alumina gel, and the mass ratio of the seed crystal to kaolin is 0.1-10:100.
11. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the crystallized product in the step (3) is calcined to obtain a microspherical material with a burning loss of less than 3% and containing 5-60% of Y-type molecular sieve.
12. The method for improving the activity of the catalytic cracking catalyst according to claim 1, wherein the mass ratio of silicon tetrachloride to the material after the calcination of the crystallized product in the step (3) is 0.01 to 0.7:1, preferably the mass ratio is 0.05-0.4: 1.
13. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the roasting step in step (3) is performed in a pretreatment furnace comprising a feed section, a roasting section and a discharge section, the pretreatment furnace having a total length of 0.5 to 5 m, an inner diameter of 0.01 to 1 m and a roasting temperature of 100 to 1000 ℃.
14. The method for improving the activity of a catalytic cracking catalyst according to claim 13, wherein the pretreatment furnace comprises a heating system and a ventilation system, the heating system is arranged on the outer layer of the pretreatment furnace in a furnace tile jacket mode, the ventilation system is arranged on the inner wall of the pretreatment furnace, and the ventilation system can input dry gas, nitrogen or water vapor into the interior of the pretreatment furnace.
15. The method for increasing the activity of a catalytic cracking catalyst according to claim 13, wherein the angle α of the pretreatment furnace feed section to the pretreatment furnace body is greater than 10 ° and less than 90 °, and the angle β of the pretreatment furnace body to the horizontal is greater than 10 ° and less than 90 °.
16. The method for improving the activity of the catalytic cracking catalyst according to claim 13, wherein a shaft rotating device is arranged at the top of the pretreatment furnace to control the rotation of the furnace body of the pretreatment furnace, and the rotation frequency is 10-80 Hz/min.
17. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the downer isomorphous substitution reactor is divided into a buffer zone and a reaction zone from top to bottom, a catalyst inlet is arranged at the top of the buffer zone, an atomizer communicated with the catalyst inlet is arranged at the upper part of the buffer zone, a nitrogen inlet carrying silicon tetrachloride is arranged at the bottom of the reaction zone, a discharge port is arranged at the upper part of the reaction zone, and the inner diameter ratio of the buffer zone to the reaction zone is 1:1 to 4:1, wherein the heights of the buffer zone and the reaction zone are respectively and independently 0.2-1 meter.
18. The method for increasing the activity of a catalytic cracking catalyst according to claim 17, wherein the inner diameter ratio of said buffer zone to said reaction zone is 1:1 to 3:1; preferably, a heating sleeve or a heating belt is arranged on the outer wall of the downer isomorphous substitution reactor; preferably, the diameter of the cavity of the reaction zone is 0.05-0.5 m.
19. The method for improving the activity of the catalytic cracking catalyst according to claim 17, wherein the atomizer is made of stainless steel and comprises a plurality of symmetrically distributed gas holes, the diameter of each gas hole is 80-200 um, and the gas pressure in the atomizer is 0.1-6 MPa.
20. The method for improving the activity of the catalytic cracking catalyst according to claim 1, wherein in the step (3), the isomorphous substitution reaction temperature is 200-900 ℃, preferably 300-600 ℃, the contact time of the material after the roasting of the crystallized product and the silicon tetrachloride gas is 0.1-60 min, the silicon tetrachloride is carried into the reactor by taking nitrogen as carrier gas, and the proportion of the silicon tetrachloride to the total carrier gas is as follows: 0.1 to 100 percent.
21. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein in the step (4), the acid used in the acid exchange is one or more of sulfuric acid, oxalic acid, hydrochloric acid, phosphoric acid and nitric acid, preferably hydrochloric acid and/or nitric acid, and the rare earth used in the rare earth exchange is one or more of rare earth chloride, rare earth nitrate, rare earth hydroxide, rare earth carbonate and rare earth sulfate, preferably rare earth chloride and/or rare earth nitrate.
22. The method for improving the activity of a catalytic cracking catalyst according to claim 1, wherein the catalyst Na is 2 O is not more than 0.4%, and the specific surface is 200-500 m 2 Per gram, pore volume of 0.40-0.55 mL/g, unit cell constant of
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