CN112717985B - Filter residue and preparation method thereof, catalytic cracking catalyst and preparation method thereof - Google Patents
Filter residue and preparation method thereof, catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN112717985B CN112717985B CN201911033218.6A CN201911033218A CN112717985B CN 112717985 B CN112717985 B CN 112717985B CN 201911033218 A CN201911033218 A CN 201911033218A CN 112717985 B CN112717985 B CN 112717985B
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- 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to the field of preparation and utilization of filter residue, and discloses filter residue and a preparation method thereof, and a catalytic cracking catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Mixing acid and the filtrate obtained after the modification of the molecular sieve to obtain a first material, wherein the pH value of the first material is 5-7; (2) settling and filtering the first material; (3) Roasting the filter residue obtained by filtering in the step (2), wherein the roasting temperature is not higher than 450 ℃. The method provided by the invention has the advantages that the filtrate obtained after the molecular sieve modification is independently recycled, the preparation method is simple, the influence of strong acid and sodium silicate in other filtrates on the filtrate obtained after the molecular sieve modification is avoided, the performance of the filtrate is damaged, and the cracking performance of the catalyst can be improved by applying the filter residue prepared by the method to a catalytic cracking catalyst.
Description
Technical Field
The invention relates to the field of preparation and utilization of filter residue, in particular to filter residue and a preparation method thereof, and a catalytic cracking catalyst and a preparation method thereof.
Background
In China, the dosage of molecular sieve cracking catalysts for cracking petroleum hydrocarbons is increasing. The main raw materials for producing the molecular sieve cracking catalyst comprise water glass, sodium hydroxide, aluminum hydroxide, kaolin, hydrochloric acid, sulfuric acid, liquid alkali, ammonium sulfate, ammonium chloride, rare earth chloride and other conventional inorganic acids, alkalis, salts and the like. The product is a spherical catalyst with the particle size of 60-80 microns, and the particle size of the molecular sieve of the intermediate product is about 1 micron. The production of molecular sieve cracking catalysts consists of three process stages coupled to each other: hydrothermal synthesis of NaY molecular sieve, modification of molecular sieve and preparation of catalyst.
(1) The whole synthesis process of the NaY molecular sieve is carried out in a liquid phase, only crystallization mother liquor and washing waste liquor are discharged from the process, and the two waste liquors contain the same alkaline substance, namely low-modulus water glass (sodium silicate). The traditional production process is to discharge the waste water into a trench and discharge the waste water into a catalyst sewage plant for treatment. When the alkaline silicate meets acidic sewage discharged by other devices, gelation is easy to occur immediately, the water content of the gel is over 90 percent, and the sludge treatment load of a sewage treatment plant is increased.
(2) The molecular sieve modification process comprises the processes of ion exchange, pre-drying, ultra-stabilized roasting at high temperature and the like. The ion exchange is carried out in an aqueous phase or wet state, and the main waste to be discharged is a waste liquid containing ammonium salts. In some cases, waste liquid containing rare earth salt is discharged, the waste liquid is alkaline (pH is 7-9), and the material form of the processes of drying and ultra-stabilizing is solid powder. The solid powder is discharged to a sewage treatment plant along with the waste liquid, and the acidic waste liquid meets the alkaline waste liquid discharged in the synthesis process of the molecular sieve to form gel.
(3) The preparation process of the catalyst comprises the processes of gelling, spray drying and forming, roasting, washing, exchanging, airflow drying and the like, and waste discharged in the processes is collected and filtered to obtain catalyst filter residue. Almost no foreign matter is produced in the gelling process; the dust generated by spray drying, forming and roasting is partially discharged into a sewage treatment system after being collected by water, solid-containing waste liquid generated by post-treatment such as washing, exchange and the like also enters the sewage treatment system, and the mixture of the waste liquid is filtered to obtain the catalyst waste residue.
The three waste water filtrates constitute a main source of a large amount of solid waste residues in a catalyst factory. TheseSolid waste residues, mainly SiO 2 、Al 2 O 3 、Re 2 O 3 、Na 2 O and Fe 2 O 3 And containing Cl - 、SO 4 2- 、F - 、Ca 2+ 、Mg 2+ 、P、K + 、TiO 2 Etc. these components may exist in the form of molecular sieve particles, catalyst particles, silica alumina gel, clay, etc. Most of the existing catalyst factories use entrusted treatment and landfill methods to treat the waste residues. Thus, not only the environment is polluted, but also the resources are seriously wasted. The waste residues are reasonably treated, so that a large amount of raw materials can be saved, the preparation cost of the catalyst is reduced, and the pollution of a catalyst plant to the surrounding environment is reduced.
In the prior art, some reports about treatment and reuse of industrial waste residues are provided, such as physical methods of pressure forming, briquetting and the like, and CN1051523A discloses a method for preparing waste residues into building materials and fillers. Further, as a technique for extracting useful components from waste slag, for example, CN1044635A discloses a method for extracting rare earth from rare earth-containing waste slag. However, extraction of useful components is not effective for various components, and it does not allow complete digestion of the waste residues, even increasing the amount of waste residues due to the treatment process.
CN101767026A discloses a preparation method of catalytic material containing Y type molecular sieve, which comprises: (1) Adding a certain amount of aluminum source, silicon source and acid into solid waste residue of a catalyst factory, mixing and pulping to make the solid waste residue stable and uniform, wherein the solid waste residue comprises the following components: mainly containing 2.5-8wt% of Na 2 O,25-65wt% SiO 2 18-55wt% of Al 2 O 3 (ii) a (2) Drying the slurry and roasting at 600-1100 deg.c for 0.5-4 hr; (3) Performing ion exchange on the material obtained in the step (2) and sodium salt, hydrochloric acid or ammonium salt to remove harmful ions contained in waste residues; (4) Adding the material obtained in the step (3) into water glass, sodium oxide, sulfuric acid and a guiding agent, uniformly stirring to obtain a crystallized mixture, and crystallizing the crystallized mixture in a reaction kettle at the temperature of 90-120 ℃ for 8-48 hours. And washing and drying the crystallized product to obtain the catalytic material containing the Y-type molecular sieve. And the prior artCompared with the method for preparing the catalyst by recycling the catalyst waste residue in the operation, the method provided by the invention effectively eliminates the adverse effect of harmful metal ions in the waste residue, and improves the catalytic performance of the catalytic material containing the Y-type molecular sieve.
CN102242270A discloses a method for recovering rare earth from catalyst waste residue, which comprises reacting rare earth-containing catalyst waste residue with acid to dissolve rare earth and some metal ions, filtering and separating, separating rare earth from filtrate by solvent extraction separation method or oxalic acid precipitation method, removing aluminum by aluminum salt, mixing raffinate and filtered solid, reacting with aluminum salt and alkaline substance, aging, filtering, washing and drying to obtain catalyst waste residue with specific surface area not less than 150m 2 The pore volume is not less than 0.2ml/g, and the most probable pore diameter is 4-20nm, thereby achieving the purpose of waste utilization.
CN103058218A discloses a preparation method of NaY molecular sieve, which comprises: (1) Mixing catalyst filter residue, naY molecular sieve gel, kaolin and a binder to prepare slurry, and performing spray drying on the obtained slurry to obtain microspheres, wherein the use amount of the catalyst filter residue on a dry basis is 10-60 parts by weight, the use amount of the NaY molecular sieve gel on the dry basis is 5-20 parts by weight, and the use amount of the kaolin on the dry basis is 20-70 parts by weight relative to 100 parts by weight of the microspheres; (2) Carrying out gas phase crystallization on the microspheres obtained in the step (1), and then roasting; (3) Mixing the product obtained after roasting with a guiding agent, sodium silicate and sodium hydroxide, carrying out hydrothermal crystallization, and then filtering, washing and drying the product obtained after hydrothermal crystallization. The method provided by the invention can realize the recycling of the catalyst filter residue and reduce the dosage of kaolin in the process of preparing the NaY molecular sieve by in-situ crystallization.
CN103408091A discloses a method for recovering rare earth oxalate precipitation wastewater, which is characterized in that the rare earth oxalate precipitation wastewater and hydrochloric acid are prepared into solution, wherein the concentration of oxalate is 0.01-10g/L, and H is + The concentration is 3.5-6mol/L. The method disclosed by the method prepares the oxalic acid rare earth precipitation wastewater and hydrochloric acid into a solution for back extraction of rare earth from the rare earth-loaded extraction solution, thereby solving the problem of wastewater discharge and savingThe acid required to strip the rare earth and the oxalic acid required to ultimately precipitate the rare earth are disclosed.
In the prior art, the catalyst waste residue is used as the raw material and the catalyst carrier of different types of molecular sieves and the method for extracting the rare earth elements, so that the utilization of the catalyst waste residue is more reasonable, but more harmful substances contained in the waste residue are not effectively utilized, and the performance of the molecular sieves or the catalyst can be influenced.
CN102896000A discloses a utilization method of waste residue in catalyst production, which comprises the following steps: (1) drying the catalyst waste residue; (2) Contacting the material obtained in the step (1) with an ammonium salt aqueous solution or an alkali metal salt aqueous solution for ion exchange, washing and filtering; (3) Roasting the material obtained in the step (2) at 450-750 ℃, and then exchanging, washing and filtering; (4) And (4) mixing the material obtained in the step (3), molecular sieve waste residues and water, pulping, filtering, drying, and roasting at 500-700 ℃ to obtain the active carrier. And pulping and spray drying the active carrier, the ultrastable Y-type molecular sieve, the alumina binder and the clay to obtain the cracking catalyst. The obtained catalytic cracking catalyst has high cracking activity, high activity stability and low yield of dry gas and coke.
Although the prior art discloses a method for utilizing waste residues generated in catalyst production, all waste residues (molecular sieve waste residues and catalyst waste residues) are treated uniformly, and the characteristics that preparation equipment and process are relatively complex and filter residues are not efficiently utilized are achieved.
Disclosure of Invention
The invention aims to provide a method for preparing filter residue by quickly settling and filtering filtrate obtained in a molecular sieve modification process, a catalytic cracking catalyst and a preparation method thereof. The preparation method of the filter residue provided by the invention reduces the sewage discharge pressure, and the prepared filter residue is used in the catalytic cracking catalyst, so that the preparation cost of the catalyst can be reduced.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a filter residue, comprising:
(1) Mixing acid and the filtrate obtained after the modification of the molecular sieve to obtain a first material, wherein the pH value of the first material is 5-7;
(2) Settling and filtering the first material;
(3) Roasting the filter residue obtained by filtering in the step (2), wherein the roasting temperature is not higher than 450 ℃;
based on the total amount of the filtrate after the modification of the molecular sieve, the filtrate after the modification of the molecular sieve contains 40 to 90 weight percent of water and 4 to 30 weight percent of Al 2 O 3 4-20% by weight of SiO 2 1-10% by weight of Re 2 O 3 And 0.1-5 wt% of Na 2 O。
Preferably, the method further comprises: mixing the modified molecular sieve filtrate with a magnesium-containing compound to obtain a mixed material, and mixing the mixed material with the acid to obtain the first material.
Preferably, the mass ratio of the filtrate after the molecular sieve modification to the magnesium-containing compound is (1-20): 1, preferably (1-10): 1, more preferably (5-10): 1.
the second aspect of the present invention provides a filter residue obtained by the above preparation method, wherein the filter residue comprises, based on the total amount of the filter residue: 35-50% by weight of Al 2 O 3 25-40% by weight of SiO 2 5-15% by weight of Re 2 O 3 0.1-5 wt% of Na 2 O。
In a third aspect, the present invention provides a process for preparing a catalytic cracking catalyst, the process comprising: the binder, the molecular sieve and the filter residue provided by the invention and optionally clay are beaten to obtain a catalyst slurry, and the catalyst slurry is spray dried and optionally calcined.
The fourth aspect of the present invention provides a catalytic cracking catalyst prepared by the above preparation method.
In the research process, the inventor of the invention finds that the performance of the modified molecular sieve can be reduced if the modified filtrate is corroded by other waste liquid (sodium silicate, strong acid) and the like, and the amount of the filter residue is increased due to the increase of the using amount of the catalyst, so that the generation speed of the filter residue is urgently needed to be increased under the conditions of the existing process and equipment. The preparation method provided by the invention can accelerate the production speed of the filter residue, improve the purity of the filter residue and efficiently utilize the filter residue to the catalytic cracking catalyst so as to improve the cracking performance of the catalyst.
Compared with the existing waste residue utilization method, the preparation method of the filter residue provided by the invention has the following advantages:
(1) According to the invention, the filtrate obtained after the molecular sieve modification is separately recycled, the preparation method is simple, and the problem that the filtrate obtained after the molecular sieve modification is influenced by strong acid and sodium silicate in other filtrates to destroy the performance of the filtrate is avoided;
(2) The filtrate after the modification of the molecular sieve has less impurity ions, so that the filtrate is prevented from being used together with other filtrate to cause the exchange modification of excessive used media, and the waste and pollution are avoided;
(3) The filter residue prepared by the method is applied to a catalytic cracking catalyst, so that the cracking performance of the catalyst can be improved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a method for preparing filter residue, comprising:
(1) Mixing acid and the filtrate obtained after the modification of the molecular sieve to obtain a first material, wherein the pH value of the first material is 5-7;
(2) Settling and filtering the first material;
(3) Roasting the filter residue obtained by filtering in the step (2), wherein the roasting temperature is not higher than 450 ℃;
based on the total amount of the filtrate after the modification of the molecular sieve, the filtrate after the modification of the molecular sieve contains 40 to 90 weight percent of water and 4 to 30 weight percent of Al 2 O 3 4-20% by weight of SiO 2 1-10% by weight of Re 2 O 3 And 0.1-5 wt% of Na 2 O。
The modified filtrate of the molecular sieve with the composition can be used in the preparation method provided by the invention, the source of the modified filtrate of the molecular sieve is not particularly limited, and the modified filtrate of the molecular sieve can comprise a large amount of filtrate generated after filtration of various molecular sieves (including Y-type molecular sieves, ZSM-5 molecular sieves, beta molecular sieves and the like) in the modification process.
Preferably, the filtrate after the molecular sieve modification does not include the filtrate (containing sodium silicate) generated in the synthesis process of the molecular sieve (such as NaY molecular sieve).
Preferably, the filtrate after the molecular sieve modification contains 40-80 wt% of water and 10-30 wt% of Al based on the total amount of the filtrate after the molecular sieve modification 2 O 3 5-20% by weight of SiO 2 3-6% by weight of Re 2 O 3 And 0.1-4 wt% of Na 2 And O. More preferably, the filtrate after molecular sieve modification contains 40-65 wt% of water and 20-30 wt% of Al based on the total amount of the filtrate after molecular sieve modification 2 O 3 10-20% by weight of SiO 2 3-5% by weight of Re 2 O 3 And 2-4 wt% of Na 2 O。
In addition to the above composition, the filtrate after the modification of the molecular sieve of the present invention may also contain other substances, and preferably, the filtrate after the modification of the molecular sieve further contains P 2 O 5 、Fe 2 O 3 F, caO, mgO and SO 4 2- At least one of (1). P in the filtrate obtained after the molecular sieve is modified by the method 2 O 5 、Fe 2 O 3 F, caO, mgO, and SO 4 2- Preferably, P is based on the total amount of the filtrate after the molecular sieve modification 2 O 5 、Fe 2 O 3 、F、CaO、MgO、SO 4 2- Each independently in an amount of 0 to 2 wt%.
The filtrate after the molecular sieve modification is generally alkaline, and preferably, the pH value of the filtrate after the molecular sieve modification is not less than 7, preferably 7 to 9, and more preferably 8 to 9.
According to the present invention, preferably, the method further comprises: mixing the modified molecular sieve filtrate with a magnesium-containing compound to obtain a mixed material, and mixing the mixed material with the acid to obtain the first material. The inventor of the invention discovers in the research process that the filtrate obtained by modifying the molecular sieve is mixed with a magnesium-containing compound and then is mixed with acid, so that the subsequent sedimentation is facilitated, and the obtained filter residue is used in a catalytic cracking catalyst, so that the cracking performance of the catalyst is further improved.
According to a preferred embodiment of the present invention, the mass ratio of the filtrate after the molecular sieve modification to the magnesium-containing compound is (1-20): 1, preferably (1-10): 1, more preferably (5-10): 1.
according to a preferred embodiment of the present invention, the magnesium-containing compound is a magnesium salt, preferably at least one selected from the group consisting of magnesium hydroxide, magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium phosphate, and more preferably magnesium hydroxide.
According to a preferred embodiment of the invention, the pH of the first mass is between 6 and 7. By adopting the preferred embodiment, the free rare earth ions and aluminum ions are more favorably agglomerated, settled and filtered.
Preferably, the acid is selected from at least one of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, and citric acid; further preferred are oxalic acid and sulfuric acid, and more preferred is a molar ratio of oxalic acid to sulfuric acid of 1-10:1, for example 3-4. The sulfuric acid is strong acid, the speed of neutralizing alkali is high, the change of the pH value is high, the precipitation speed is high, the oxalic acid has a complexing effect, the precipitation speed of ions is enhanced, and the oxalic acid and the sulfuric acid are matched to obtain a better precipitation effect.
The acid may be introduced in the form of a solution, for example, the sulfuric acid may be introduced in the form of dilute sulfuric acid. In the present embodiment, the example of the concentration of 75% by mass is given as an example, and the present invention is not limited thereto.
The invention has wide selection range of the sedimentation condition of the step (2), and preferably, the sedimentation time of the step (2) is 1 to 8 hours, more preferably 1 to 3 hours.
According to the present invention, step (1) and step (2) may be performed in a settling tank. The modified filtrate of the molecular sieve can be injected into the settling pond according to the size specification of the settling pond in proportion by a person skilled in the art.
The filtration mode in step (2) is not particularly limited in the present invention, and may be performed according to the conventional technical means in the art, for example, the filtration in step (2) may be performed in a filtration apparatus such as a belt filter, a plate-and-frame filter, a filtration type screw centrifuge, etc., which are well known to those skilled in the art.
According to the present invention, preferably, the calcination time in step (3) is 0.5 to 8 hours.
According to a preferred embodiment of the present invention, the firing conditions in step (3) include: the temperature is 250-400 ℃ and the time is 1-3 hours. More preferably, the temperature of the calcination is 300-380 ℃. With this preferred embodiment, the catalytic cracking performance of the obtained filter residue can be further improved.
The preparation method provided by the invention also preferably comprises the step of crushing and grinding the roasted product obtained in the step (3). The conditions for the pulverization and the grinding are not particularly limited in the present invention. The equipment used in the comminution and grinding process may be well known to those skilled in the art. For example, the comminution may be carried out in a shear or a mill, and the grinding may be carried out in a ball mill or a sand mill.
The second aspect of the present invention provides a filter residue obtained by the above preparation method, wherein the filter residue comprises, based on the total amount of the filter residue: 35-50% by weight of Al 2 O 3 25-40% by weight of SiO 2 5-15% by weight of Re 2 O 3 0.1-5 wt% of Na 2 O。
Preferably, the filter residue further contains MgO, and the content of MgO is 0-10 wt%, more preferably 3-9 wt%, based on the total amount of the filter residue. The source of MgO in the filter residue may be a filtrate obtained by modifying a molecular sieve, or may be a magnesium-containing compound introduced in a preferred embodiment.
Preferably, the filter residue further comprises: fe 2 O 3 、CaO、F、SO 4 2- And P 2 O 5 At least one of (1), fe 2 O 3 、CaO、F、SO 4 2- And P 2 O 5 Each independently is present in an amount of 0 to 5wt%, more preferably 0.1 to 3 wt%.
Preferably, the pore volume of the filter residue is 0.35-0.6mL/g, and more preferably 0.36-0.5mL/g. The filter residue provided by the invention has larger pore volume, and is applied to the catalytic cracking catalyst, so that the catalytic performance of the catalytic cracking catalyst is improved.
In a third aspect, the present invention provides a process for preparing a catalytic cracking catalyst, the process comprising: the binder, the molecular sieve and the filter residue provided by the invention and optionally clay are pulped to obtain catalyst slurry, and the catalyst slurry is spray-dried and optionally calcined.
The term "optionally" as used herein means that the substance may or may not be used, and the operation may or may not be performed.
According to a preferred embodiment of the invention, the method comprises: pulping the binder, the molecular sieve, the filter residue and the clay to obtain catalyst slurry, and performing spray drying and roasting on the catalyst slurry.
According to a specific embodiment of the present invention, the preparation method may further include: washing, filtering and drying after the roasting to obtain the catalytic cracking catalyst.
The spray drying, roasting, washing, filtering and drying are the prior art, and the invention has no special requirements and is not described in detail herein.
The invention has wide selection range of the binder, preferably, the binder is selected from at least one of pseudo-boehmite, aluminum sol, silica sol, magnesium aluminum sol, zirconium sol and titanium sol, and is preferably the pseudo-boehmite and the aluminum sol.
According to a preferred embodiment of the present invention, the binder is pseudo-boehmite and alumina sol, and the preparation method of the catalytic cracking catalyst comprises: mixing the aluminum sol and the pseudo-boehmite to obtain slurry, adding the filter residue and optionally clay, adding acid for acidification, and finally adding the molecular sieve. By adopting the preferred embodiment, the filter residue can be more favorably prepared into the macroporous material which has larger pore distribution, so that the molecular sieve cracking is more accurate, the obtained product is more excellent, particularly, the yield of light oil and gasoline is further increased, the yield of heavy oil is further reduced, the cracking degree of the catalyst is increased, and the coke selectivity is improved.
The acidification in the present invention is not particularly limited, and can be carried out according to a method conventionally used in the art. The acid used for acidification in the present invention is selected widely, and may be, for example, inorganic acids conventionally used in the art, including but not limited to hydrochloric acid. The acid to pseudoboehmite weight ratio is preferably 0.01 to 0.1.
The clay of the present invention is a clay raw material well known to those skilled in the art, and any kind of commonly used clay can be used in the present invention, and for the present invention, the clay is preferably one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. For the present invention, preferably the clay is kaolin and/or halloysite.
In the present invention, the molecular sieve is a well-known molecular sieve raw material, and any molecular sieve commonly used in the art can be used in the present invention, and for the present invention, it is preferable that the molecular sieve is at least one of Y zeolite, ZSM-5 zeolite, and beta zeolite. More preferably REY, REHY, REUSY, USY, and by gas phase chemical method (SiCl) 4 Al removal and Si supplement method), liquid phase chemical method ((NH) 4 ) 2 SiF 6 Aluminum extraction and silicon supplement) and other methods, and ZSM-5 type and beta type zeolites with other high silicon-aluminum ratios or the mixture thereof. Preferably, the molecular sieve is a REY molecular sieve.
According to the method for preparing a catalytic cracking catalyst of the present invention, the solid content of the catalyst slurry is preferably 15 to 45% by weight, more preferably 30 to 45% by weight, for example 30 to 40% by weight.
According to a preferred embodiment of the present invention, the binder, the molecular sieve, the filter residue and the clay are used in amounts such that the molecular sieve content of the prepared catalytic cracking catalyst is 25 to 50 wt%, preferably 25 to 35 wt%, on a dry basis, based on the dry weight of the catalytic cracking catalyst (the weight after 1 hour of calcination at a dry weight of 800 ℃); the clay content is from 0 to 50% by weight, preferably from 0 to 32% by weight, based on dry substance; the binder content, calculated as oxide, is from 10 to 30% by weight, preferably from 15 to 28% by weight; the content of filter residue is 2-50 wt%, preferably 15-44 wt% on a dry basis.
The fourth aspect of the present invention provides a catalytic cracking catalyst prepared by the above preparation method. The catalytic cracking catalyst prepared by the preparation method provided by the invention has the advantages of strong heavy oil cracking capability, higher gasoline yield, higher light oil yield and liquid yield, and lower coke selectivity.
The present invention will be described in detail below by way of examples. The specifications of the raw materials used in the examples are as follows:
kaolin: with a solids content of 72% by weight, manufactured by china kaolin, inc (suzhou).
Sulfuric acid, oxalic acid: analyzing and purifying;
aluminum sol: al (aluminum) 2 O 3 22 wt%, produced by Qilu Branch of China petrochemical catalyst, inc.;
pseudo-boehmite: solid content 72 wt%, shandong aluminum industries, china;
the molecular sieve used in the preparation of the catalytic cracking catalyst is REY type molecular sieve: produced by Qilu division of China petrochemical catalyst, the solid content is 80 weight percent, and the rare earth content is 17.4 weight percent;
the composition of the catalyst is determined by calculating the feeding amount of each raw material.
The analysis method comprises the following steps:
(1) The pore volume and the abrasion index were measured by the methods RIPP28-90 and RIPP29-90 in "petrochemical analysis method, RIPP test method" (edited by Yangdi, published by scientific Press, 1990).
Example 1
This example illustrates the preparation of the filter residue and the catalytic cracking catalyst.
Preparing filter residue:
(1) Injecting the filtrate (pH 8.5) after the molecular sieve modification into 20m 3 The composition of the filtrate after molecular sieve modification in the settling tank of (1) is shown in table 1; adding oxalic acid and dilute sulfuric acid (mass concentration is 75%) solution with the molar ratio of 3;
(2) Roasting the filter cake obtained in the step (1) in a shuttle kiln for 2 hours at 350 ℃;
(3) And (3) grinding the roasted material obtained in the step (2) on a ball mill for 8 hours to obtain a molecular sieve filter residue finished product, wherein the composition and the properties of the molecular sieve filter residue finished product are shown in the following table 2.
Preparation of catalytic cracking catalyst:
adding 3.64kg of alumina sol into a reaction kettle, stirring, adding 2.78kg of pseudo-boehmite, adding 4.82kg of decationized water (also called acidic water in the invention), stirring for 40min, adding 5.17kg of filter residue, stirring for 60min, adding 0.4kg of hydrochloric acid with the concentration of 22 wt%, stirring for 30min, finally adding 11.76kg of REY molecular sieve slurry (4.38 kg of molecular sieve and 7.38kg of decationized water), and stirring for 30min to obtain catalyst slurry. And (4) carrying out spray drying on the catalyst slurry to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain the catalytic cracking catalyst C-1. The catalyst composition and properties are shown in table 3.
Comparative example 1
Preparation of catalytic cracking catalyst:
adding 3.64kg of alumina sol into a reaction kettle, stirring, adding 2.78kg of pseudo-boehmite, adding 4.82kg of decationized water (also called as acidic water in the invention), stirring for 40min, adding 5.14kg of kaolin, stirring for 60min, adding 0.4kg of hydrochloric acid with the concentration of 22 wt%, stirring for 30min, finally adding 11.76kg of REY molecular sieve slurry (4.38 kg of molecular sieve and 7.38kg of decationized water), and stirring for 30min to obtain catalyst slurry. And (4) carrying out spray drying on the catalyst slurry to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain the catalytic cracking catalyst D-1. The catalyst composition and properties are shown in table 3.
Comparative example 2
The residue and the catalytic cracking catalyst were prepared according to the method of example 1, except that the calcination condition in the step (2) was that calcination was carried out at 480 ℃ for 2 hours. To obtain the catalytic cracking catalyst D-2. The catalyst composition and properties are shown in table 3.
Example 2
This example illustrates the preparation of filter residue and a catalytic cracking catalyst.
The residue was prepared according to the method of example 1.
Preparation of catalytic cracking catalyst:
adding 3.64kg of alumina sol into a reaction kettle, stirring, adding 2.78kg of pseudo-boehmite, adding 5.88kg of decationized water (also called as acidic water in the invention), stirring for 40min, adding 5.87kg of filter residue, stirring for 60min, adding 0.4kg of hydrochloric acid with the concentration of 22 wt%, stirring for 30min, finally adding 10kg of REY molecular sieve slurry (wherein the molecular sieve is 3.75kg, the decationized water is 6.25 kg), and stirring for 30min to obtain the catalyst slurry. And (4) carrying out spray drying on the catalyst slurry to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing each time by using decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres, and drying for 2 hours at constant temperature of 120 ℃ to obtain the catalytic cracking catalyst C-2. The catalyst composition and properties are shown in table 3.
Example 3
This example illustrates the preparation of the filter residue and the catalytic cracking catalyst.
The residue was prepared according to the method of example 1.
Preparation of catalytic cracking catalyst:
adding 3.64kg of alumina sol into a reaction kettle, stirring, adding 2.78kg of pseudo-boehmite, adding 5.89kg of decationized water (also called acidic water in the invention), stirring for 40min, adding 3.08kg of filter residue and 2.78kg of kaolin, stirring for 60min, adding 0.4kg of hydrochloric acid with the concentration of 22 wt%, stirring for 30min, finally adding 10kg of REY molecular sieve slurry (wherein the molecular sieve is 3.75kg, the decationized water is 6.25 kg), and stirring for 30min to obtain the catalyst slurry. And (4) carrying out spray drying on the catalyst slurry to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing each time by using decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres, and drying at constant temperature of 120 ℃ for 2 hours to obtain the catalytic cracking catalyst C-3. The catalyst composition and properties are shown in table 3.
Example 4
This example illustrates the preparation of filter residue and a catalytic cracking catalyst.
The residue was prepared according to the method of example 1.
Preparation of catalytic cracking catalyst:
adding 3.64kg of alumina sol into a reaction kettle, stirring, adding 2.78kg of pseudo-boehmite, adding 5.91kg of decationized water (also called as acidic water in the invention), stirring for 40min, adding 1.40kg of filter residue and 4.44kg of kaolin, stirring for 60min, adding 0.4kg of hydrochloric acid with the concentration of 22 wt%, stirring for 30min, finally adding 10kg of REY molecular sieve slurry (wherein the molecular sieve is 3.75kg, the decationized water is 6.25 kg), and stirring for 30min to obtain the catalyst slurry. And (4) carrying out spray drying on the catalyst slurry to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain the catalytic cracking catalyst C-4. The catalyst composition and properties are shown in table 3.
Example 5
This example illustrates the preparation of filter residue and a catalytic cracking catalyst.
Preparing filter residue:
(1) Injecting the modified molecular sieve filtrate (pH of 8) into 20m 3 The composition of the filtrate after molecular sieve modification in the settling tank of (1) is shown in table 1; adding oxalic acid and dilute sulfuric acid (mass concentration is 75%) solution with the molar ratio of 4Filtering by a machine;
(2) Roasting the filter cake obtained in the step (1) in a shuttle kiln for 1.5 hours at 380 ℃;
(3) And (3) grinding the roasted material obtained in the step (2) on a ball mill for 8 hours to obtain a molecular sieve filter residue finished product, wherein the composition and the properties of the molecular sieve filter residue finished product are shown in the following table 2.
Preparation of catalytic cracking catalyst:
the catalytic cracking catalyst C-5 was obtained by following the procedure for the preparation of the catalytic cracking catalyst described in example 1. The catalyst composition and properties are shown in table 3.
Example 6
This example illustrates the preparation of filter residue and a catalytic cracking catalyst.
Preparing filter residue:
(1) Injecting the filtrate (pH 7.5) after molecular sieve modification into 20m 3 The composition of the filtrate after molecular sieve modification in the settling tank of (1) is shown in table 1; adding oxalic acid and dilute sulfuric acid (mass concentration is 75%) solution with the molar ratio of 4 to the filtrate, gradually adjusting the pH value to 6, settling for 5 hours, and filtering by a plate and frame filter;
(2) Roasting the filter cake obtained in the step (1) in a shuttle kiln for 3 hours at 300 ℃;
(3) And (3) grinding the roasted material obtained in the step (2) on a ball mill for 8 hours to obtain a molecular sieve filter residue finished product, wherein the composition and the properties of the molecular sieve filter residue finished product are shown in the following table 2.
Preparation of catalytic cracking catalyst:
the catalytic cracking catalyst C-6 was obtained by following the procedure for the preparation of the catalytic cracking catalyst described in example 1. The catalyst composition and properties are shown in table 3.
Example 7
This example illustrates the preparation of filter residue and a catalytic cracking catalyst.
Preparation of filter residue:
(1) The modified molecular sieve filtrate (same as example 1) was poured into 20m 3 In the sedimentation tank; adding magnesium hydroxide into the filtrate, wherein the mass ratio of the filtrate to the magnesium hydroxide is 10:1; then oxalic acid and dilute sulfuric acid (75% by mass concentration) with the molar ratio of 3) Gradually adjusting the pH value of the solution to 7, settling for 1 hour, and filtering by a plate and frame filter;
(2) Roasting the filter cake obtained in the step (1) in a shuttle kiln for 2 hours at 350 ℃;
(3) And (3) grinding the roasted material in the step (2) for 8 hours on a ball mill to obtain a molecular sieve filter residue finished product, wherein the composition and the properties are shown in the following table 2.
Preparation of catalytic cracking catalyst:
the catalytic cracking catalyst C-7 was obtained by following the procedure for the preparation of the catalytic cracking catalyst described in example 1. The catalyst composition and properties are shown in table 3.
Example 8
This example illustrates the preparation of filter residue and a catalytic cracking catalyst.
Preparing filter residue:
(1) The modified molecular sieve filtrate (same as example 1) was poured into a 20m column 3 In the sedimentation tank; adding magnesium hydroxide into the filtrate, wherein the mass ratio of the filtrate to the magnesium hydroxide is 5:1; then adding oxalic acid and dilute sulfuric acid (mass concentration is 75%) solution with the molar ratio of 3;
(2) Roasting the filter cake obtained in the step (1) in a shuttle kiln for 2 hours at 350 ℃;
(3) And (3) grinding the roasted material in the step (2) for 8 hours on a ball mill to obtain a molecular sieve filter residue finished product, wherein the composition and the properties are shown in the following table 2.
Preparation of catalytic cracking catalyst:
the preparation of the catalytic cracking catalyst described in example 1 was carried out to obtain catalytic cracking catalyst C-8. The catalyst composition and properties are shown in table 3.
TABLE 1 composition of the filtrate after modification of the molecular sieves
| Example numbering | Example 1 | Example 5 | Example 6 |
| Al 2 O 3 To weight percent | 27.2 | 25.6 | 24.7 |
| SiO 2 To weight percent | 16.2 | 13.5 | 14.9 |
| Re 2 O 3 To weight percent | 4.2 | 3.8 | 3.6 |
| Na 2 O, wt.% | 2.8 | 3.1 | 3.5 |
| MgO, by weight% | 0.6 | 0.4 | 0.3 |
| Fe 2 O 3 To weight percent | 0.5 | 0.8 | 1.0 |
| CaO, by weight% | 1.5 | 1.4 | 1.6 |
| SO 4 2- To weight percent | 0.9 | 1.2 | 1.5 |
| P 2 O 5 To weight percent | 0.7 | 0.8 | 0.5 |
| F - To weight percent | 0.2 | 0.4 | 0.3 |
Note: the filtrate contains water and other trace impurities except the components.
TABLE 2 composition and Properties of the Filter residue
Note: the content unit of the components in the filter residue is 'wt%'. The solids content was determined by calcination at 800 ℃ for 1 h.
TABLE 3 composition and Properties of the catalysts
Note: in Table 3, the contents of the alumina sol and the pseudo-boehmite are both calculated as alumina.
Test example 1
This test example was used to evaluate the performance of the catalytic cracking catalyst provided by the present invention.
The catalyst is aged and deactivated for 17 hours at 800 ℃ by 100 percent of water vapor. The loading of the catalyst is 9g, the reaction raw material is Wu-MI-Sanyuan oil, and the raw materials are shown in Table 4. The reaction temperature was 500 ℃ and the catalyst-to-oil ratio (by weight) was 5, and the measured catalyst performance parameters are shown in Table 5.
Wherein, the conversion rate = gasoline yield + liquefied gas yield + dry gas yield + coke yield;
the yield of light oil = gasoline yield + diesel oil yield;
liquid yield = liquefied gas yield + gasoline yield + diesel oil yield;
coke selectivity = coke yield/conversion;
TABLE 4
TABLE 5
As can be seen from table 5, compared with the catalytic cracking catalyst prepared by the prior art, the catalytic cracking catalyst prepared by using the filter residue prepared by the method instead of kaolin has better and better heavy oil cracking performance, higher conversion rate, gasoline yield and liquid yield, and lower heavy oil yield and diesel yield under the premise of the same usage amount of the molecular sieve; as can be seen from example 2 using a lower amount of molecular sieve, the prepared catalyst C-2 still has better and better heavy oil cracking performance and higher conversion rate and gasoline yield than comparative example 1.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (24)
1. A preparation method of filter residue comprises the following steps:
(1) Mixing acid and the filtrate obtained after the modification of the molecular sieve to obtain a first material, wherein the pH value of the first material is 5-7;
(2) Settling and filtering the first material;
(3) Roasting the filter residue obtained by filtering in the step (2), wherein the roasting temperature is not higher than 450 ℃;
based on the total amount of the filtrate after the modification of the molecular sieve, the filtrate after the modification of the molecular sieve contains 40 to 65 weight percent of water and 20 to 30 weight percent of Al 2 O 3 10-20% by weight of SiO 2 3-5% by weight of Re 2 O 3 And 2-4 wt% of Na 2 O；
The method further comprises the following steps: mixing the modified molecular sieve filtrate with a magnesium-containing compound to obtain a mixed material, and mixing the mixed material with the acid to obtain the first material;
the mass ratio of the filtrate after the molecular sieve modification to the magnesium-containing compound is (1-20): 1.
2. the production method according to claim 1,
the mass ratio of the filtrate after the molecular sieve modification to the magnesium-containing compound is (1-10): 1.
3. the production method according to claim 2,
the mass ratio of the filtrate after the molecular sieve modification to the magnesium-containing compound is (5-10): 1.
4. the production method according to claim 1,
the magnesium-containing compound is at least one selected from magnesium hydroxide, magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium phosphate.
5. The production method according to claim 4,
the magnesium-containing compound is magnesium hydroxide.
6. The preparation method of claim 1, wherein the pH value of the filtrate after the molecular sieve modification is not less than 7;
and/or the pH value of the first material is 6-7;
and/or, the acid is selected from at least one of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and citric acid.
7. The preparation method of claim 6, wherein the pH value of the filtrate after the molecular sieve modification is 7-9;
and/or, the acid is oxalic acid and sulfuric acid, and the molar ratio of the oxalic acid to the sulfuric acid is 1-10:1.
8. the preparation method of claim 7, wherein the pH value of the filtrate after the molecular sieve modification is 8-9.
9. The production method according to any one of claims 1 to 8, wherein the settling time in step (2) is 1 to 8 hours.
10. The method according to claim 9, wherein the settling time in the step (2) is 1 to 3 hours.
11. The production method according to any one of claims 1 to 8, wherein the calcination in the step (3) is carried out for 0.5 to 8 hours.
12. The production method according to any one of claims 1 to 8,
the roasting condition in the step (3) comprises the following steps: the temperature is 250-400 ℃ and the time is 1-3 hours.
13. The production method according to any one of claims 1 to 8,
the filtrate after the molecular sieve modification also contains P 2 O 5 、Fe 2 O 3 F, caO, mgO, and SO 4 2- At least one of;
taking the total amount of the filtrate after the modification of the molecular sieve as a reference, P 2 O 5 、Fe 2 O 3 、F、CaO、MgO、SO 4 2- Each independently in an amount of 0 to 2 wt%.
14. The filter residue obtained by the preparation method according to any one of claims 1 to 13, wherein the filter residue comprises, based on the total amount of the filter residue: 35-50% by weight of Al 2 O 3 25-40% by weight of SiO 2 5-15% by weight of Re 2 O 3 0.1-5 wt% of Na 2 O; the filter residue also contains MgO, and the content of MgO is 0-10 wt% based on the total amount of the filter residue.
15. Filter residue according to claim 14, wherein,
the content of MgO is 3-9 wt% based on the total amount of the filter residue.
16. Filter residue according to claim 14, wherein,
the filter residue still includes: fe 2 O 3 、CaO、F、SO 4 2- And P 2 O 5 At least one of (1), fe 2 O 3 、CaO、F、SO 4 2- And P 2 O 5 Each independently in an amount of 0 to 5 wt%.
17. Filter residue according to any one of claims 14-16, wherein,
the pore volume of the filter residue is 0.35-0.6mL/g.
18. The filter residue according to claim 17, wherein,
the pore volume of the filter residue is 0.36-0.5mL/g.
19. A process for preparing a catalytic cracking catalyst, the process comprising: pulping a binder, a molecular sieve and the filter residue of any one of claims 14 to 18 and optionally clay to obtain a catalyst slurry, spray drying and optionally calcining the catalyst slurry.
20. The production method according to claim 19, wherein the binder is selected from at least one of pseudo-boehmite, aluminum sol, silica sol, magnesium aluminum sol, zirconium sol, and titanium sol;
and/or the clay is at least one of kaolin, halloysite, montmorillonite, diatomite, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite;
and/or the molecular sieve is at least one of Y zeolite, ZSM-5 zeolite and beta zeolite.
21. The production method according to claim 20, wherein the binder is pseudo-boehmite and an aluminum sol;
and/or the clay is kaolin and/or halloysite.
22. The preparation method according to any one of claims 19 to 21, wherein the binder, the molecular sieve, the filter residue and the clay are used in amounts such that the prepared catalytic cracking catalyst has a molecular sieve content of 25 to 50 wt.% on a dry basis, based on the weight of the catalytic cracking catalyst on a dry basis; the clay content is 0-50 wt.% on a dry basis; the content of the binder calculated by oxide is 10-30 wt%; the content of the filter residue is 2-50 wt% based on dry basis.
23. The preparation method of claim 22, wherein the binder, the molecular sieve, the filter residue and the clay are used in amounts such that the prepared catalytic cracking catalyst has a molecular sieve content of 25-35 wt% on a dry basis, based on the weight of the catalytic cracking catalyst on a dry basis; the clay content is 0-32 wt% on a dry basis; a binder content of 15-28 wt.% calculated as oxide; the content of the filter residue is 15-44 wt% on a dry basis.
24. A catalytic cracking catalyst obtained by the production method according to any one of claims 19 to 23.
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