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  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/80—Mixtures of different zeolites
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
  • B01J35/51—Spheres
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/026—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/20—Faujasite type, e.g. type X or Y
  • C01B39/24—Type Y
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J2029/062—Mixtures of different aluminosilicates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
  • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/37—Acid treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • 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
  • B01J29/088—Y-type faujasite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/66—Pore distribution
  • B01J35/67—Pore distribution monomodal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/66—Pore distribution
  • B01J35/69—Pore distribution bimodal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0027—Powdering
  • B01J37/0045—Drying a slurry, e.g. spray drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/30—Ion-exchange

Definitions

• the invention relates to a heavy oil catalytic cracking catalyst with high heavy oil conversion ability and a preparation method thereof. Specifically, it is a catalytic cracking catalyst suitable for blending residual oil and a preparation method thereof. Background technique
• the catalytic cracking unit is an important secondary processing method for crude oil, and its comprehensive product distribution determines the economic benefits of the refinery.
• FCC catalysts are required to have stronger heavy oil conversion capacity and high value product selectivity.
• Y-type molecular sieves are the main providers of cracking activity of heavy oil cracking catalysts. The stability of their activity and the high level of cracking activity are the key factors determining the conversion capacity of heavy oil in FCC catalysts.
• the rare earth ions can be positioned as much as possible in the rare earth ion modification process of the molecular sieve to inhibit the dealuminization of the molecular sieve skeleton during the water vapor aging process, thereby improving the structural stability and activity stability of the molecular sieve framework.
• Patent ZL200410058089.3 introduces a preparation method of rare earth modified Y type molecular sieve, which is to adjust the pH value of the system to 8 ⁇ 11 by using alkali solution after the end of the rare earth exchange reaction, and then carry out a conventional subsequent treatment process according to the method.
• the prepared molecular sieve rare earth ions are all located in the small cage (sodal stone cage);
• Chinese patent ZL97122039.5 describes a preparation method of ultra-stable Y zeolite, which comprises contacting a Y-type zeolite with an acid solution and a solution containing ammonium ions, and performing high-temperature steam treatment.
• the acid is used in an amount of 1.5 to 6 moles of hydrogen ion per mole of the framework aluminum, the acid solution concentration is 0.1 to 5 equivalents per liter, and the temperature at which the Y-type zeolite is contacted with the acid solution is 5 to 100 ° C, and the contact time is 0.5 to 72 hours.
• the weight ratio of the Y-type zeolite to the ammonium ion is 2 to 20.
• the modification method involved in the patent needs to add an ammonium ion-containing solution, the purpose of which is to reduce the content of sodium oxide in the molecular sieve or to reduce the damage of the acid gas to the molecular sieve structure during the roasting process.
• the FCC catalyst prepared by using the molecular sieve has the heavy oil conversion ability. The characteristics of strong and light oil yield are high; however, the molecular sieve modification technology has the following technical defects: 1) A large amount of ammonium ions are added during the preparation process, and the ammonium ions finally enter the atmosphere or sewage, thereby increasing the ammonia nitrogen pollution and the pollution control cost. ;
• the patent also mentions that the Y-type zeolite can be introduced into the rare earth ion by ion exchange at the same time as or after the contact with the ammonium ion-containing solution.
• the ammonium ion and the rare earth ion have a competitive reaction, ammonium.
• Ion will be excellent First occupying the rare earth ion site 3 ⁇ 4, increasing the resistance of rare earth ion exchange into the molecular sieve cage, and reducing the utilization of rare earth ions.
• Chinese patent ZL02103909.7 describes a preparation method of rare earth-containing ultra-stable Y molecular sieve, which is prepared by subjecting NaY molecular sieve to one-time roasting once, and is characterized in that NaY molecular sieve is placed in ammonium ion solution at 25 ⁇ Chemical dealuminization treatment at 100 ° C, oxalic acid and / or oxalate in the chemical dealumination complexing agent, treatment time 0.5 ⁇ 5 hours, then adding rare earth solution, stirring, to produce rare earth precipitate containing rare earth oxalate, by It is filtered, washed with water to form a filter cake, and then hydrothermally treated to obtain a molecular sieve product.
• the molecular sieve prepared by the method has certain anti-vanadium pollution ability, its activity stability and cracking activity are low, and the development trend of heavy oil quality and inferior quality of the raw material oil cannot be satisfied.
• This is mainly related to the positional distribution of rare earth ions in the molecular sieve super cage and sodalite cage during molecular sieve modification.
• the method clarifies that the rare earth ions exist in the molecular sieve system in two forms, that is, some rare earth ions enter the sodalite cage in the form of ions, and the other rare earth ions are rare earth oxides (the precursor is rare earth oxalate, which is converted into oxidation by subsequent calcination).
• the rare earth is dispersed on the surface of the molecular sieve, which reduces the stable supporting effect of the rare earth ions on the molecular sieve structure. At the same time, there is a large amount of ammonia nitrogen pollution in the method, and the added oxalic acid and or oxalate are more harmful to the environment and human body. Big.
• CN200410029875.0 discloses a preparation method of rare earth ultrastable Y type zeolite, characterized in that the method comprises treating zeolite with a mixed solution of rare earth salt and citric acid or a mixed solution of inorganic ammonium salt, rare earth salt and citric acid.
• a step of. The method can simplify the process, and the prepared zeolite as an active component of the cracking catalyst has the advantages of reducing the olefin content of the catalytic cracking gasoline product and significantly increasing the yield of the catalytic cracking light oil product, but the method does not locate the rare earth ions of the molecular sieve. Be explained. Summary of the invention
• the object of the present invention is to provide a novel heavy oil high-efficiency conversion catalytic cracking catalyst and a preparation method thereof, which are characterized in that the heavy oil has strong conversion ability, the coke selectivity is moderate, and the target product has high yield.
• the invention provides a novel heavy oil high-efficiency conversion catalytic cracking catalyst, which is characterized in that the catalyst composition contains 2 ⁇ 50% by weight of ultra-stable rare earth Y type molecular sieve, 0.5 ⁇ 30% by weight of one or several other molecular sieves, 0.5 ⁇ 70 % by weight of clay, 1.0 to 65% by weight of high temperature resistant inorganic oxide and 0.01 to 12.5% by weight of oxidized rare earth, wherein ultra stable rare earth Y type molecular sieve refers to super stable rare earth Y type molecular sieve containing oxidized rare earth 0.5 to 25 weight% , the sodium oxide is not more than 1.2% by weight, the crystallinity is 40 ⁇ 75%, and the unit cell parameter is 2.449nm ⁇ 2.472nm.
• the preparation process of the ultra-stable rare earth cerium type molecular sieve comprises rare earth exchange and dispersion pre-exchange, wherein the rare earth exchange and dispersion pre-exchange
• the order of the rare earth exchange and the dispersion pre-exchange is continuous, and there is no roasting process between them;
• the dispersion pre-exchange means that the concentration of the molecular sieve slurry is adjusted to a solid content of 80-400 g/L, and 0.2% by weight to 7% by weight is added.
• Dispersing agent for dispersion pre-exchange exchange temperature is 0 ⁇ 100 ° C, exchange time is 0.1 ⁇ 1.5 hours; dispersion pre-exchange process, the dispersant is selected from Tianjing powder, boron , One or more of urea, ethanol, polyenamide, acetic acid, oxalic acid, adipic acid, acid, hydrochloric acid, nitric acid, citric acid, salicylic acid, tartaric acid, benzoic acid, starch; rare earth exchange, dispersion pre- No ammonium salts were used in the exchange.
• the invention also provides a preparation method of the heavy oil catalytic cracking catalyst:
• the molecular sieve slurry can be washed and filtered without being filtered. It can also be washed and filtered.
• the RE 2 O3/Y zeolite (mass) is preferably 0.005 to 0.25, preferably 0.01 to 0.20;
• the exchange temperature is 0 to 100 ° C, preferably 60 to 95 ° C; 2.5 to 6.0, preferably 3.5 to 5.5, the exchange time is 0.1 to 2 hours, preferably 0.3 to 1.5 hours;
• the dispersant is added in an amount of 0.2% by weight to 7% by weight, preferably 0.2% by weight.
• % ⁇ 5wt% exchange temperature is 0 ⁇ 100°C, optimally 60 ⁇ 95 ⁇ ; exchange time is 0.1 ⁇ 1.5 hours.
• the modified molecular sieve slurry is filtered and washed with water to obtain a filter cake, and the obtained filter cake is flash-dried to have a moisture content of 30% to 50%, and finally calcined, and the calcination conditions can be carried out under common conditions, for example, at 350 ° C to 700 ° ° C, 0 ⁇ 100% water vapor roasting for 0.3 ⁇ 3.5 hours, preferably at 450 °C ⁇ 650 °C, 15 ⁇ 100% water vapour roasting for 0.5 ⁇ 2.5 hours, that is, "one-to-one baking" ultra-stable rare earth sodium Y molecular sieve .
• the "single-baked" ultra-stable rare earth sodium Y molecular sieve is subjected to the second exchange and the second calcination to obtain the ultra-stable rare earth Y-type molecular sieve described in the present invention, wherein the second exchange and the second baking are
• the ammonium salt exchange sodium reduction and ultra-stabilization processes familiar in the industry are not limited in this regard.
• the exchange process of rare earth exchange and dispersion pre-exchange can be carried out by tank exchange, belt exchange and/or filter cake exchange; In this case, it is possible to divide the rare earth compound solution into several parts under the premise that the total amount of the rare earth is constant, and perform tank exchange, belt exchange and/or cake exchange, that is, multiple exchanges.
• the dispersant in the process of dispersing the pre-exchange process, can be divided into several parts under the premise of the total amount of dispersant, for tank exchange, belt exchange and/or filter cake exchange; rare earth exchange and dispersion pre-pretreatment When switching to multiple exchanges, the two types of exchanges can be crossed.
• the rare earth compound of the present invention is rare earth chloride or rare earth nitrate or rare earth sulfate, preferably rare earth chloride or nitric acid. Rare earth.
• the rare earth of the present invention may be a cerium-rich or cerium-rich rare earth, or may be pure cerium or pure cerium.
• the dispersing agent in the dispersion pre-exchange process of the present invention is selected from the group consisting of ffl cyanine powder, boric acid, urea, ethanol, polyacrylamide, acetic acid, oxalic acid, adipic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid.
• ffl cyanine powder boric acid, urea, ethanol, polyacrylamide, acetic acid, oxalic acid, adipic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid.
• tartaric acid, benzoic acid, and starch preferably two or more.
• the other molecular sieves in the catalyst composition of the present invention are one or more selected from the group consisting of Y zeolite, L zeolite, ZSM-5 zeolite, ⁇ zeolite, aluminum phosphate zeolite, ⁇ zeolite, preferably cerium type zeolite, ZSM-5.
• the clay according to the present invention is one or more selected from the group consisting of kaolin, halloysite, montmorillonite, sepiolite, perlite, etc.; said high temperature resistant inorganic oxide is one or more selected from the group consisting of A1 2 0 3, Si0 2, Si0 2 -Al 2 0 3, A1P0 4, its precursor comprising a silica-alumina gel, silica sol, alumina sol, silica-alumina composite sol, boehmite and pseudoboehmite.
• the spraying conditions of the present invention are conventional operating conditions for preparing a cracking catalyst, and the present invention is not limited thereto; the post-treatment process is the same as the prior art, and includes catalyst calcination, water washing, drying, etc., wherein the roasting is preferably a spray microsphere.
• the sample is calcined at 200 ° C to 700 ° C, preferably 300 ° C ⁇ 650 ° C, time 0. 05-4 hours, preferably 0. 1-3. 5 hours; water washing conditions are preferably: water / catalyst weight is 0 ⁇ 5. 3 ⁇ 0. 5 ⁇ 35, The water wash temperature is 20 ° C ⁇ 100 ° C, the time is 0. 1 ⁇ 0. 3 hours.
• NaY molecular sieve NaY-1 (silicon to aluminum ratio 4.8, crystallinity 92%), NaY-2 (silicon to aluminum ratio 4.1, crystallinity)
• Ultra-stable one-to-one baking molecular sieve sample Crystallinity 60%, sodium oxide 4.3m%, produced by Lanzhou Petrochemical Company Catalyst Factory.
• Rare earth solution rare earth chloride (rare earth oxide 277.5 g / liter), rare earth nitrate (rare earth oxide 252 g / liter), all industrial products, from the catalyst plant of Lanzhou Petrochemical Company.
• Tianjing powder, boric acid, urea, ethanol, polyacrylamide, oxalic acid, adipic acid, acetic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid, tartaric acid, starch are all chemically pure; ammonium chloride, nitric acid Ammonium, ammonium sulfate, ammonium oxalate are industrial products.
• the exchange reaction was carried out for 0.3 hours, and the obtained filter cake was flash-dried to have a moisture content of 30% to 50%, and finally calcined at 70% of water vapor and 670 ° C for 1.0 hour to obtain "one-and-one-baked" rare earth sodium Y.
• a reaction kettle with a heating jacket add 500 grams (dry basis) of ultra-stable rare earth sodium lanthanum molecular sieve and a certain amount of deionized water to prepare a slurry with a solid content of 120g/L, and add 120g.
• reaction vessel equipped with a heating mantle
• the band exchange conditions are: 35g oxalic acid It is a solution with pH value of 3.4, and the temperature is raised to 85 ° C, and the vacuum degree of the belt filter is 0.04; then the obtained filter cake is flash-dried to have a moisture content of 30% to 50%, and finally 10% water vapor and 510 Torr. Under the calcination for 2.0 hours, the "one-and-one-baked" ultra-stable rare earth sodium Y was obtained.
• the obtained filter cake was flash-dried to have a moisture content of 30% to 50%, and finally calcined at 60% water vapor and 560 Torr for 2 hours to prepare "one-and-one-baked" rare earth sodium strontium.
• 500 g (dry basis) and deionized water of "one-and-one-baked" ultra-stable rare earth sodium Y molecular sieve were added to prepare a slurry having a solid content of 280 g/L, and 130 g of ammonium sulfate was added.
• the belt exchange conditions were as follows: The rare earth nitrate solution was heated to 88 ° C, the exchange pH was 4.7, the rare earth nitrate was added in a RE 2 03/Y zeolite (mass) of 0.04, and the belt filter vacuum was 0.03; the resulting filter cake was then flash dried. The water content is 30% ⁇ 50%, and finally calcined at 80% water vapor and 53CTC for 1.5 hours to obtain "one-to-one baking" ultra-stable rare earth sodium Y"-cross-baked" ultra-stable rare earth sodium strontium.
• the method for preparing the REUSY molecular sieve was similar to the method shown in Example 3 except that hydrochloric acid and oxalic acid were not added, and the same as in Example 3, the obtained ultra-stable rare earth Y type molecular sieve number was F-1, and the obtained catalyst number was F. Comparative example 2
• the comparative example uses the molecular sieve preparation method described in CN200510114495.1 to investigate the reaction performance of the molecular sieve.
• the catalyst preparation process was the same as in Example 5.
• This comparative example uses the molecular sieve preparation method described in CN97122039.5, and the catalyst preparation process is the same as in Example 3.
• deionized water and 3000 g (dry basis) of NaY-1 molecular sieve were added to prepare a slurry having a solid content of 90 g/L, and the mixture was heated to 80 ° C with stirring, and 59 g of hydrochloric acid was added thereto, and the temperature was adjusted.
• the comparative molecular sieve sample was designated as G-1.
• micro-reaction activity The sample was pretreated at 800 ° C under 100% water vapor for 4 hours.
• the reaction raw material was Dagang light diesel oil, the reaction temperature was 460 ° C, the reaction time was 70 seconds, the catalyst loading was 5.0 g, the weight ratio of the agent oil was 3.2, and the total conversion rate was used as the micro-reaction activity.
• ACE heavy oil microreactor The reaction temperature is 530 ° C, the ratio of agent to oil is 5, and the feedstock oil is 30% vacuum residue of Xinjiang oil.
• the physicochemical properties of the ultra-stable rare earth Y type molecular sieve obtained in the examples and comparative examples of the present invention are shown in Table 1.
• the analysis results show that: Compared with the comparative example, the new molecular sieve has the characteristics of good structural stability and small particle size.
• Table 4 shows the evaluation results of the catalyst B riser. Compared with the comparative catalyst G, the total liquid of the catalyst of the present invention is increased by 0.97 percentage points, the light oil yield is increased by 0.77 percentage points, and the gasoline property is equivalent. Table 4 Evaluation results of catalyst riser
• One of the main active components of the novel heavy oil catalyst of the present invention is a high cracking active stable rare earth ultrastable Y type molecular sieve, which uses a dispersing agent to predisperse NaY molecular sieve in a rare earth modified preparation process, and reduces the molecular sieve.
• the degree of agglomeration between the particles makes the surface of the molecular sieve more contact with the rare earth ions, which reduces the resistance of the rare earth ions during the exchange process, causes the rare earth ions to exchange more into the molecular sieve cage, and migrates to the sodium during the subsequent steam roasting process.
• Stone cage The structural stability and activity stability of the molecular sieve are improved. Dilute 10.

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• 2011
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  • 2012-04-13 US US14/364,536 patent/US9844772B2/en active Active

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