Process for treating a glue solution and preparation of glue sludge and catalytic cracking catalyst

Abstract

The present application relates to the field of catalytic cracking catalyst, and discloses a glue liquid treatment method and a preparation method of glue residue and catalytic cracking catalyst, which comprises the following steps: (1) breaking the glue liquid; (2) beating the material obtained in step (1) and then washing; (3) finely grinding the material obtained after washing.The glue liquid treatment method provided by the present application can quickly dry the glue liquid and efficiently wash away impurities such as sodium oxide in the glue liquid, which not only reduces the amount of solid waste and recovery cost, has little environmental pollution, and plays a good role in forming a green closed-loop preparation process of solid catalyst, but also efficiently utilizes the Y-type molecular sieve component, replaces part of the molecular sieve and the binder, effectively reduces the preparation cost of the catalyst, and the synthesized catalyst has the effect of improving the cracking performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalytic cracking catalyst, in particular to a method for treating glue liquid, and a method for preparing catalytic cracking catalyst using glue residue obtained by treating glue liquid. BACKGROUND

[0002] In China, the amount of molecular sieve cracking catalyst used for cracking petroleum hydrocarbons is increasing. The main raw materials for producing molecular sieve cracking catalyst include water glass, sodium hydroxide, aluminum hydroxide, kaolin, hydrochloric acid, sulfuric acid, liquid alkali, ammonium sulfate, ammonium chloride, and conventional inorganic acids, bases, and salts such as chlorinated rare earth. The product is a spherical catalyst with a diameter of 60-80 microns, and the intermediate product is a molecular sieve with a particle size of about 1 micron. The production of molecular sieve cracking catalyst consists of three interrelated process stages: hydrothermal synthesis of NaY molecular sieve, modification of molecular sieve, and catalyst manufacturing.

[0003] (1) The modification process of molecular sieve includes ion exchange, pre-drying, and ultra-stabilization calcination at high temperature. Ion exchange is carried out in an aqueous or wet state, and the main waste discharge is ammonium salt-containing waste liquid. In some cases, rare earth salt-containing waste liquid is also discharged. The material form in the processes of drying and ultra-stabilization is solid powder. These solid powders are discharged together with the waste liquid into the sewage treatment plant.

[0004] (2) The catalyst manufacturing process includes gelation, spray drying and molding, calcination, washing, exchange, and air flow drying. The waste discharged from these processes is collected and filtered to obtain catalyst filter residue. The gelation process produces almost no external discharge; the dust generated during spray drying and molding and calcination is partially discharged into the sewage treatment system after being captured by water, and the solid-containing waste liquid generated during washing and exchange is also discharged into the sewage treatment system. The mixture of these waste liquids is filtered to obtain catalyst waste residue.

[0005] The filter of the above wastewater constitutes the main source of a large amount of solid waste residue in catalyst plants. These solid waste residues, mainly composed of SiO2, Al2O3, Re2O3, Na2O, and Fe2O3, also contain Cl - , SO4 2- , F - , Ca 2+ , Mg 2+ , P, K + , TiO2, etc., which may exist in the form of molecular sieve particles, catalyst particles, silica-alumina gel, clay, etc. At present, most catalyst plants use the method of entrusting disposal for landfill or send them to brick factories or ceramic factories for treatment. In this way, not only does it pollute the environment, but it also wastes a lot of resources. Properly disposing of these waste residues not only saves a large amount of raw materials, thereby reducing the cost of catalyst preparation, but also reduces the pollution of the surrounding environment by the catalyst plant.

[0006] There are some reports on the treatment and reuse of industrial waste slag in the prior art, such as using physical methods such as pressure forming and briquetting, CN1051523A discloses a method for preparing waste slag into building materials and fillers. For example, CN1044635A discloses a method for extracting rare earth from waste slag containing rare earth. However, extracting useful components cannot be effective for all components, and cannot completely digest the waste slag, and even increases the amount of waste slag due to the treatment process.

[0007] The method disclosed in US4226837A uses an alkali metal hydroxide solution to dissolve silica containing waste fly ash at 60-110°C to form an alkali metal silicate, separates the undecomposed components with activated carbon or oxidizing agent, reacts with an alkali metal aluminate at room temperature and crystallizes at 70-100°C for 8-49 hours to obtain Y zeolite.

[0008] US8614159B2 discloses a FCC catalyst additive for cracking of petroleum feedstocks and a method for preparing the same. The FCC catalyst additive of the present invention comprises at least one zeolite, at least one clay, at least one binder, phosphorus in the form of P2O5, and at least one Group IVB metal compound. The FCC catalyst additive of the present invention has hydrothermal stability, i.e., the surface area of the substrate is improved even after various hydrothermal treatments. The FCC catalyst additive of the present invention can be used in combination with conventional FCC catalysts used for catalytic cracking to selectively increase propylene and liquefied petroleum gas production.

[0009] CN201010503633.6 The present application provides a preparation method of ZSM-5 molecular sieve, which comprises crystallizing a slurry containing a silicon source, an aluminum source, an alkali agent, a template agent and water under the crystallization conditions of generating ZSM-5 molecular sieve, wherein 0.1-20 wt% of the silicon source calculated as SiO2 and 0.1-60 wt% of the aluminum source calculated as Al2O3 are derived from catalyst sludge, the rest of the aluminum source is a soluble aluminum salt, and the rest of the silicon source is at least one of silica gel, water glass solution, silica sol and silica gel; in the catalyst sludge, the content of SiO2 is 20-60 wt%, the content of Al2O3 is 15-40 wt%, the content of Na2O is 0-30 wt%, and the content of rare earth oxide is 0-10 wt%. The method provided by the present application can make full use of the colloids formed by silicon and aluminum compounds in the catalyst sludge.

[0010] CN201410327613.6 discloses a method for preparing glass ceramic using petroleum catalyst waste residue. It uses petroleum catalyst waste residue, dolomite, feldspar and additives as raw materials to prepare high value-added glass ceramic products by high temperature melting method. The maximum utilization rate of petroleum catalyst waste residue in the disclosed scheme is 90%, which greatly reduces the land cost, construction and maintenance cost of the petroleum catalyst waste residue, avoids the pollution of petroleum catalyst waste residue to the surrounding land environment, water and air, and is conducive to saving land resources and protecting the environment. The main raw material of the invention is solid waste, the raw material cost is low, the preparation method is simple, and it is conducive to industrialized production and popularization. The glass ceramic prepared by the method has high strength and good texture, and can be well applied in the production of building decoration materials, industrial wear-resistant and corrosion-resistant materials and handicrafts.

[0011] CN102242270A discloses a method for recovering rare earth from catalyst waste residue. The rare earth and some metal ions are dissolved by reacting the catalyst waste residue containing rare earth with acid. After filtration and separation, the rare earth in the filtrate is separated by solvent extraction separation method or oxalic acid precipitation method, and the aluminum is removed in the form of aluminum salt. The raffinate and the filtered solid are mixed and reacted with aluminum salt and alkaline substance, and then aged, filtered, washed and dried to obtain a mesoporous-porous material with a specific surface area not less than 150 m 2 / g, a pore volume not less than 0.2 ml / g, and a most probable pore diameter of 4-20 nm, achieving the purpose of waste utilization.

[0012] The above prior art methods for using catalyst waste residue as raw material and catalyst carrier of different types of molecular sieve and extracting rare earth elements make the utilization of catalyst waste residue more reasonable, but do not effectively utilize the harmful substances contained in the waste residue, which may affect the performance of the molecular sieve or the catalyst.

[0013] CN201410374282.1 relates to a method for efficient utilization of catalytic cracking catalyst sludge. The method first activates the sludge, and then synthesizes ultrafine Y-type molecular sieve by hydrothermal crystallization method under the action of structure directing agent. By adjusting the molecular sieve synthesis conditions and sludge pretreatment conditions, the crystal structure, specific surface area and particle size of the obtained molecular sieve can be easily adjusted; the obtained product has high specific surface area and stable structure. The synthesis of Y-type molecular sieve from catalytic cracking catalyst sludge provides a new way for the reuse of FCC catalyst sludge, realizes the greenization of the catalyst production process and the effective recycling of silicon and aluminum resources, fully utilizes the sludge, is economic and environmentally friendly, and has strong practical application value.

[0014] CN1150301C discloses a petroleum cracking catalyst containing catalyst plant waste residue and a preparation method thereof. The catalyst plant waste residue is used to replace part of the carrier filler such as natural clay or full synthetic carrier in the cracking catalyst to completely digest the catalyst plant waste residue, reduce environmental pollution and reduce the cost of the catalyst. The catalyst plant waste residue containing silicon and / or aluminum is the waste residue of the catalyst plant of the petroleum cracking catalyst variety, and the total content of SiO2 and Al2O3 in the dry basis composition is greater than or equal to 50% by weight. The physical form of the waste residue includes petroleum cracking catalyst particles, silica gel or silica alumina gel, alumina, and clay substances including kaolin and metakaolin. + 、H + 、NH4 + or rare earth ions in ionic form, including Y-type zeolite and ZSM-5 zeolite, silica gel or silica alumina gel, alumina, and clay substances including kaolin and metakaolin.

[0015] Although the above prior art discloses a method for utilizing catalyst production waste residue, all waste residues (molecular sieve waste residue and catalyst waste residue) are uniformly treated, and the preparation equipment and process are relatively complex, and the characteristics of high-efficiency utilization of the waste residue are not achieved. SUMMARY

[0016] The purpose of the present application is to overcome the problem of inefficient utilization of glue residue in the prior art, and to provide a glue liquid treatment method and a preparation method of glue residue and catalytic cracking catalyst. The glue liquid treatment method provided by the present application efficiently treats the glue liquid generated during the preparation of the catalyst and the modification of the molecular sieve, and the glue residue prepared has excellent performance and can be used as the active component and carrier of the catalytic cracking catalyst. The preparation cost of the catalyst is reduced.

[0017] To achieve the above purpose, the first aspect of the present application provides a glue liquid treatment method, which comprises the following steps:

[0018] (1) breaking the glue liquid;

[0019] (2) beating the material obtained in step (1) and then washing it;

[0020] (3) finely grinding the material obtained after washing;

[0021] In step (1), the breaking is carried out according to step (1-1) and / or step (1-2).

[0022] Step (1-1) includes low-temperature drying of the glue liquid, and the low-temperature drying conditions include a drying medium temperature of 100-250°C and an outlet temperature of 60-120°C.

[0023] The step (1-2) comprises beating the glue liquid, and the obtained slurry has a solid content of 10-20 wt%, and the slurry is dried at a high temperature, and the drying medium has a temperature of above 300 DEG C.

[0024] The second aspect of the present application provides the glue residue obtained by the above treatment method, and the glue residue comprises, based on the total amount of the dry glue residue, 15-30 wt% of Al2O3, 30-50 wt% of SiO2, 5-15 wt% of Re2O3, 0.1-2 wt% of Na2O, 1-10 wt% of SO4 2- , 1-2 wt% of Fe2O3 and 1-5 wt% of Cl - .

[0025] It can be known that the glue residue further comprises some other elements, such as phosphorus, calcium and magnesium, and the present application does not particularly limit the elements due to their small content.

[0026] The sum of the content of each component of the glue residue in the present application is 100%.

[0027] Preferably, the glue residue has a particle size DV(0.5) of not more than 6 microns and a particle size DV(0.9) of not more than 10 microns.

[0028] The third aspect of the present application provides a preparation method of a catalytic cracking catalyst, and the method comprises: beating a binder, a molecular sieve and the above glue residue and optionally clay to obtain a catalyst slurry, and spray drying and optionally calcining the catalyst slurry.

[0029] The glue liquid treatment method provided by the present application has the following advantages compared with the existing waste residue utilization method:

[0030] (1) The glue liquid can be quickly dried, and the impurities such as sodium oxide in the glue liquid can be efficiently washed away, the Y-type molecular sieve component in the glue liquid can be efficiently utilized, and part of the molecular sieve and the binder can be replaced, thereby effectively reducing the preparation cost of the catalyst, and the synthesized catalyst has the effect of improving the cracking performance;

[0031] (2) The low-temperature drying process has lower energy consumption, larger output and more uniform drying effect, the glue liquid has viscosity, if the drying effect is not good, the glue liquid is not easy to filter after washing, the sodium oxide cannot be removed, and if the drying effect is too good, the sodium oxide is easy to sinter, and the impurities such as sodium oxide cannot be removed;

[0032] (3) The glue liquid treatment method provided by the present application can reduce the amount of solid waste and the recovery cost, and the waste is currently mainly buried, the present application has small environmental pollution, and plays a good role in forming a green closed-loop preparation process of solid catalyst. DETAILED DESCRIPTION

[0033] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as exactly that endpoint. Any ranges of values disclosed herein are not to be constrained to the particular values stated at the limits of those ranges. The endpoints of the ranges of values stated are not to be construed as limiting beyond the range itself. For numeric values, the endpoints of each range, the endpoints of each range and individual point values, and individual point values can be combined with each other to generate one or more new numeric ranges, which should be considered as specifically disclosed herein.

[0034] The first aspect of the present application provides a method for treating glue liquid, the method comprising the following steps:

[0035] (1) breaking the glue liquid;

[0036] (2) beating the material obtained in step (1) and then washing it;

[0037] (3) finely grinding the material obtained after washing;

[0038] In step (1), the breaking is performed according to step (1-1) and / or step (1-2).

[0039] Step (1-1) comprises low-temperature drying of the glue liquid, and the low-temperature drying conditions include: the drying medium temperature is 100-250℃, and the outlet temperature is 60-120℃.

[0040] Step (1-2) comprises beating the glue liquid to obtain a slurry with a solid content of 10-20wt%, and then high-temperature drying the slurry, wherein the temperature of the high-temperature drying medium is above 300℃.

[0041] The method for treating glue liquid provided by the present application adopts the process combination of breaking-beating-washing-crushing, which can quickly dry the glue liquid and efficiently wash away the impurities such as sodium oxide in the glue liquid, and the glue liquid can be used in the preparation process of catalytic cracking catalyst, thereby effectively improving the performance of the prepared catalytic cracking catalyst and realizing the effective utilization of the glue liquid.

[0042] The glue liquid according to the present application has the conventional interpretation in the art, for example, the glue liquid includes the glue liquid obtained in the preparation process of catalytic cracking catalyst and / or the modification process of molecular sieve. The glue liquid according to the present application can also be referred to as glue residue, and the form of the glue liquid is not particularly limited, which is only for the purpose of distinguishing the product (referred to as glue residue in the present application).

[0043] Preferably, the glue liquid comprises 20-40 wt% of Al2O3, 30-65 wt% of SiO2, 10-25 wt% of Re2O3, and 2-10 wt% of Na2O, based on the total amount of the glue liquid in dry basis. For example, the content of Al2O3 is 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, and any range formed by any two of them; the content of SiO2 is 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, and any range formed by any two of them; the content of Re2O3 is 10 wt%, 15 wt%, 20 wt%, 25 wt%, and any range formed by any two of them; and the content of Na2O is 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%, and any range formed by any two of them.

[0044] According to a preferred embodiment of the present application, the glue liquid further comprises 1-10 wt% of SO4 2- , 0.5-2 wt% of Fe2O3, and 1-3 wt% of Cl - .

[0045] In the present application, unless otherwise specified, Re refers to rare earth elements, such as lanthanum, cerium, praseodymium, etc.

[0046] In the present application, unless otherwise specified, the dry basis weight refers to the weight after 1 hour of burning at 800℃.

[0047] The glue liquid in the present application can be a product obtained after settling and filtering of waste liquid generated in the process of preparing a catalytic cracking catalyst and / or the process of modifying a molecular sieve. Preferably, the solid content of the glue liquid is 10-25 wt%, preferably 15-20 wt%.

[0048] According to the present application, preferably, the crystallinity of the glue liquid is above 10%, preferably 10-25%. The glue liquid has a certain crystallinity, and the glue residue obtained by treating the glue liquid is used in the process of preparing a catalytic cracking catalyst, which is more conducive to improving the performance of the catalytic cracking catalyst.

[0049] The crystallinity of the glue liquid is tested by SHT 0340-1992 NaY molecular sieve crystallinity determination method.

[0050] In step (1) of the present application, the glue breaking can be performed in the manner described in step (1-1), or in the manner described in step (1-2), or partially in the manner described in step (1-1) and the remaining part in the manner described in step (1-2).

[0051] Preferably, the solid content of the obtained material in step (1-1) is 30-70 wt%, preferably 50-70 wt%. The preferred embodiment is more conducive to the cooperation with the subsequent steps, and the effective removal of Na is achieved.

[0052] According to the method provided by the application, preferably, the low-temperature drying in step (1-1) is performed under the conditions that the drying medium temperature is 120-160℃, and the outlet temperature is 80-120℃. The preferred embodiment can effectively reduce the energy consumption on the basis of ensuring the performance of the obtained sludge in the catalytic cracking catalyst.

[0053] The application does not particularly limit the time of the low-temperature drying, and the person skilled in the art can appropriately select the time according to the temperature of the low-temperature drying and the solid content of the obtained material.

[0054] The application has a wide range of choices for the low-temperature drying mode, and preferably, the low-temperature drying in step (1-1) is performed by at least one of steam drying, microwave drying and thin film drying.

[0055] The application has a wide range of choices for the drying medium of the low-temperature drying, and preferably, the drying medium can be at least one of air, oil and water vapor.

[0056] The application does not particularly limit the equipment for the beating in step (1-2), and the beating can be performed in a stirred tank or a stirred tank.

[0057] The application does not particularly limit the specific operation and conditions of the beating in step (1-2), as long as the rubber solution can be dispersed into water and can be pumped to step (2) for the next operation.

[0058] Preferably, the solid content of the slurry obtained by beating in step (1-2) is 12-16 wt%. Preferably, the water used for beating is deionized water. The deionized water can be the deionized water commonly used by the person skilled in the art, and the purpose is to not bring other impurities in the beating process.

[0059] The application has a wide range of choices for the conditions of the high-temperature drying, and preferably, the temperature of the high-temperature drying medium is above 500℃, preferably 500-600℃. The temperature of the high-temperature drying medium can refer to the temperature of the drying hot air.

[0060] According to the treatment method provided by the application, preferably, the outlet temperature of the high-temperature drying is 150-180℃.

[0061] According to the treatment method provided by the present application, the high-temperature drying method can be selected in a wide range, and preferably, the high-temperature drying method is flash drying. In the specific implementation, the flash feeding amount depends on the size of the flash drying bag.

[0062] According to a preferred embodiment of the present application, the solid content of the material obtained by the high-temperature drying is 30-70 wt%, and preferably 50-70 wt%.

[0063] According to the present application, preferably, in step (2), the beating is performed using de-cationic water; and further preferably, the solid content of the slurry obtained by the beating is 25-60 wt%, and preferably 25-35 wt%. The use of this preferred embodiment is more conducive to the sufficient washing of impurities.

[0064] Preferably, the washing medium used in step (2) is selected from at least one of ammonium sulfate, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and citric acid, and preferably ammonium sulfate and hydrochloric acid, and more preferably, the mass ratio of ammonium sulfate and hydrochloric acid (preferably with a mass concentration of 15-36%) is 1-3:1. The use of this preferred embodiment is more conducive to the effective removal of sodium and alkaline earth metals.

[0065] Preferably, the washing in step (2) results in that, in the obtained product, the content of sodium oxide is not higher than 2.5 wt% based on the total amount on a dry basis, and the content of magnesium oxide and calcium oxide is not higher than 0.5 wt%.

[0066] According to a preferred embodiment of the present application, the method further comprises filtering the product obtained by the washing to obtain a filter cake, and then beating (preferably with a solid content of 25-40 wt%) the filter cake and performing the fine grinding treatment in step (3).

[0067] The present application does not have a particular limitation on the conditions of the fine grinding treatment. The equipment used in the fine grinding process can be well known to those skilled in the art. Preferably, the fine grinding treatment in step (3) is performed in a shearing machine, a ball mill or a sand mill.

[0068] The present application does not have a particular limitation on other specific operating conditions of the fine grinding treatment, and those skilled in the art can make adaptive selection according to the specific circumstances. Preferably, the fine grinding treatment is performed to a particle size close to that of a molecular sieve particle. In the preferred case, the fine grinding treatment results in particles with a DV(0.5) of not more than 6 microns, and preferably 3-6 microns, and a DV(0.9) of not more than 10 microns, and preferably 7-10 microns.

[0069] The second aspect of the present application provides the glue residue obtained by the above-mentioned treatment method, wherein, based on the total amount of the glue residue, the glue residue comprises: 15-30 wt% of Al2O3, 30-50 wt% of SiO2, 5-15 wt% of Re2O3, 0.1-2 wt% of Na2O, 1-10 wt% of SO4 2- , 1-2 wt% of Fe2O3, and 1-5 wt% of Cl - .

[0070] Preferably, the solid content of the glue residue is 10-25 wt%.

[0071] Preferably, the crystallinity of the glue residue is more than 10%, preferably 10-25%. The preferred embodiment is more conducive to improving the performance of the catalyst when the glue residue is applied to the catalytic cracking catalyst.

[0072] Preferably, the specific surface area of the glue residue is more than 200 m 2 / g, preferably 200-280 m 2 / g. The glue residue provided by the present application has a large pore volume, which is more conducive to improving the catalytic performance of the catalytic cracking catalyst when it is applied to the catalytic cracking catalyst.

[0073] In the present application, the specific surface area of the glue residue is obtained by GB / T38691-2020 Petroleum Refining Catalyst Specific Surface Area Test Method, unless otherwise specified.

[0074] Preferably, the particle size DV(0.5) of the glue residue is not more than 6 microns, preferably 3-6 microns, and the particle size DV(0.9) is not more than 10 microns, preferably 7-10 microns.

[0075] In the present application, the DV(0.5) and DV(0.9) are obtained by Q / TSH3490901-2006 Catalytic Cracking Catalyst Particle Size Distribution Measurement Laser Particle Size Method, unless otherwise specified.

[0076] In the present application, the composition of the glue solution and the glue residue is obtained by fluorescence analysis ASTM D7085-2004e1, unless otherwise specified.

[0077] The third aspect of the present application provides a preparation method of a catalytic cracking catalyst, which comprises: slushing a binder, a molecular sieve, and the above-mentioned glue residue and optionally clay to obtain a catalyst slurry, and spray drying and optionally calcining the catalyst slurry.

[0078] The "optionally" in the present application means that the substance can be used or not used, and the operation can be performed or not performed.

[0079] According to a preferred embodiment of the present application, the method comprises: mixing the binder, the molecular sieve and the above-mentioned sludge and clay to obtain a catalyst slurry, and then spray drying and calcining the catalyst slurry.

[0080] According to a specific embodiment of the present application, the preparation method can further comprise: washing, filtering and drying after the calcining to obtain the catalytic cracking catalyst.

[0081] The spray drying, calcining, washing, filtering and drying are prior art and are not particularly required by the present application, and thus will not be described here.

[0082] The present application has a wide range of choices for the binder, and preferably, the binder is selected from at least one of pseudo-boehmite, aluminum sol, silicon sol, magnesium-aluminum sol, zirconium sol and titanium sol.

[0083] According to a preferred embodiment of the present application, the binder is pseudo-boehmite and aluminum sol, and the preparation method of the catalytic cracking catalyst comprises: mixing the aluminum sol and the pseudo-boehmite to obtain a slurry, then adding the sludge, optionally adding the clay, then adding an acid for acidification, and finally adding the molecular sieve. This preferred embodiment is more conducive to reducing the use amount of the molecular sieve, and under the same cracking capacity (gasoline yield and conversion rate), the use amount of the Y-type molecular sieve can be reduced by 10-20%, and the catalyst cost can be reduced by more than 10%.

[0084] The acidification is not particularly limited in the present application and can be performed according to the conventional technical means in the art. The type of acid used for the acidification is selected widely in the present application, and for example, can be an inorganic acid commonly used in the art, including but not limited to hydrochloric acid. The weight ratio of the acid to the pseudo-boehmite is preferably 0.01 to 0.1.

[0085] The clay in the present application is a clay raw material known to those skilled in the art, and the commonly used types of clay can be used in the present application. For the present application, preferably, the clay is one or more of kaolin, halloysite, montmorillonite, diatomite, halloysite, metahalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. For the present application, preferably, the clay is kaolin and / or halloysite.

[0086] In the present application, the molecular sieve is a raw material of molecular sieve well known in the art, and the molecular sieve species commonly used in the art can be used in the present application. Preferably, the molecular sieve is at least one of Y zeolite, ZSM-5 zeolite and beta zeolite. Further preferably, the molecular sieve is at least one of REY, REHY, REUSY, USY, Y zeolite with different silicon-aluminum ratios prepared by gas phase chemical method (SiCl4de-Al and Si supplementing method), liquid phase chemical method ((NH4)2SiF6aluminum extraction and silicon supplementing method) and other methods, and mixtures thereof, and ZSM-5 and beta zeolites with other types of high silicon-aluminum ratio or mixtures thereof. Preferably, the molecular sieve is REY molecular sieve.

[0087] According to the preparation method of the catalytic cracking catalyst of the present application, preferably, the solid content of the catalyst slurry is 15-45 wt%, further preferably 30-45 wt%, for example 30-40 wt%.

[0088] The present application does not have special limitations on the amounts of glue residue, binder, clay and molecular sieve, and a person skilled in the art can select them according to the desired composition of the catalytic cracking catalyst.

[0089] According to a preferred embodiment of the present application, the amounts of binder, molecular sieve, glue residue and clay are such that the content of the molecular sieve in the catalytic cracking catalyst prepared is 20-35 wt% on a dry basis, preferably 20-30 wt%, based on the dry weight of the catalytic cracking catalyst; the content of the clay is 0-50 wt% on a dry basis, preferably 20-40 wt%; the content of the binder is 5-30 wt% on an oxide basis, preferably 10-20 wt%; and the content of the glue residue is 2-50 wt% on a dry basis, preferably 5-25 wt%.

[0090] The present application provides a catalytic cracking catalyst prepared by the above preparation method. The glue solution treatment method provided by the present application can quickly dry the glue solution and efficiently wash impurities such as sodium oxide in the glue solution, efficiently utilize the Y-type molecular sieve component therein, replace part of the molecular sieve and binder, effectively reduce the cost of catalyst preparation, and the synthesized catalyst has the effect of improving the cracking performance.

[0091] The present application will be described in detail below by way of examples. The specifications of the raw materials used in the examples are as follows:

[0092] Kaolin: solid content 72 wt%, produced by China Kaolin Co., Ltd. (Suzhou).

[0093] Ammonium sulfate, hydrochloric acid: analytical pure.

[0094] Aluminum sol: Al2O3 content 22 wt%, produced by Sinopec Catalyst Co., Ltd. Qilu Branch.

[0095] Pseudo-boehmite: solid content 72 wt%, Shandong Aluminum Industry Co., Ltd.

[0096] The molecular sieve used in the preparation of the catalytic cracking catalyst is a REY type molecular sieve: produced by Qilu Branch, Sinopec Catalyst Co., Ltd., solid content 80 wt%, rare earth content 17.6 wt%.

[0097] The composition in the catalyst is determined according to the feeding amount of each raw material.

[0098] Unless otherwise specified, the percentage content defined in the following examples and comparative examples is mass percentage content.

[0099] Analysis method:

[0100] (1) The pore volume and attrition index are determined by RIPP 28-90 and RIPP 29-90 methods in Petroleum Chemical Industry Analysis Methods, RIPP Test Methods (Yang Cuiding, edited by Science Press, published in 1990), respectively.

[0101] (2) The bulk density is obtained by NB / SH / T 0954-2017 Catalytic Cracking Catalyst Apparent Bulk Density Determination Method.

[0102] Example 1

[0103] This example is used to illustrate the preparation of the colloidal residue and the catalytic cracking catalyst.

[0104] Preparation of colloidal residue:

[0105] (1) The wet colloidal residue A (colloid solution, composition see Table 1 below) obtained in the catalyst preparation process and the molecular sieve modification process is slurried with deionized water, and the solid content after slurry is 15%;

[0106] (2) The slurry obtained in step (1) is transported to flash drying by a centrifugal transfer pump, the drying hot air temperature is 500℃, the outlet temperature is 165℃, and the solid content after drying is 55%;

[0107] (3) The material obtained in step (2) is slurried, and the solid content is 30%, (NH4)2SO4 and 15% mass concentration hydrochloric acid are added to the slurry: the mass ratio of (NH4)2SO4 and 15% mass concentration hydrochloric acid is 2:1, after 1h of exchange, filtration is carried out by a belt filter, and the filter cake is slurried with deionized water, and the slurry solid content is 30%;

[0108] (4) The slurry material after washing in step (3) is finely ground on a ball mill for 8 hours, and finally the colloidal residue product B is obtained, and the composition and properties are shown in Table 1 below.

[0109] Preparation of catalytic cracking catalyst:

[0110] The aluminum sol was added into the reactor according to the proportion in Table 2 and stirred. Pseudo-boehmite was added, deionized water (also referred to as acidic water in the present application) was added and stirred for 40 min. The sludge product B was added and stirred for 60 min. Concentrated hydrochloric acid (22 wt.%) was added (the weight ratio of hydrochloric acid to pseudo-boehmite was 0.1) and stirred for 30 min. Finally, the REY molecular sieve slurry was added and stirred for 30 min to obtain a catalyst slurry (solid content of 34%). The catalyst slurry was spray dried to obtain catalyst microspheres. The obtained catalyst microspheres were calcined at 500°C for 1 h, washed twice, each time using 8 times the dry weight of the catalyst microspheres with deionized water, and dried at 120°C for 2 h to obtain a catalytic cracking catalyst C-1. The catalyst composition and properties are shown in Table 2. In order to compare the effects of the examples and comparative examples, some examples and comparative examples also included adding rare earth during the preparation of the catalyst slurry. The specific amount of the rare earth added is shown in Table 2. The amount of the rare earth added in Table 2 is based on the total amount of kaolin, molecular sieve, aluminum sol, sludge, and pseudo-boehmite being 100%.

[0111] Table 1 Dry basis composition and properties of the sludge before and after treatment

[0112]

[0113]

[0114] Example 2

[0115] This example is used to illustrate the preparation of a sludge and a catalytic cracking catalyst.

[0116] The sludge was prepared according to the method of Example 1. A catalytic cracking catalyst was prepared according to the proportion in Table 2 and the process of Example 1 to obtain C-2. The catalyst composition and properties are shown in Table 2.

[0117] Example 3

[0118] The sludge was prepared according to the method of Example 1. A catalytic cracking catalyst was prepared according to the proportion in Table 2 and the process of Example 1 to obtain C-3. The catalyst composition and properties are shown in Table 2.

[0119] Example 4

[0120] The residue was prepared according to the method of Example 1. The aluminum sol was added into a reaction kettle according to the proportions in Table 2, and stirred. Pseudo-boehmite was added, and deionized water (also referred to as acidic water in the present application) was added and stirred for 40 min. Concentrated hydrochloric acid (22 wt.%) was added (the weight ratio of hydrochloric acid to pseudo-boehmite was 0.1) and stirred for 30 min. Finally, the REY molecular sieve slurry was added and stirred for 30 min, to obtain a catalyst slurry (solid content of 34%). The catalyst slurry was spray dried to obtain catalyst microspheres. The catalyst microspheres were calcined at 500°C for 1 h, washed twice, each time with 8 times the dry weight of the catalyst microspheres of deionized water, and dried at 120°C for 2 h, to obtain a catalytic cracking catalyst C-4. The catalyst composition and properties are shown in Table 2.

[0121] Comparative Example 1

[0122] The aluminum sol was added into a reaction kettle according to the proportions in Table 2, and stirred. Pseudo-boehmite was added, and deionized water (also referred to as acidic water in the present application) was added and stirred for 40 min. Concentrated hydrochloric acid (22 wt.%) was added (the weight ratio of hydrochloric acid to pseudo-boehmite was 0.1) and stirred for 30 min. Finally, the REY molecular sieve slurry was added and stirred for 30 min, to obtain a catalyst slurry (solid content of 34%). The catalyst slurry was spray dried to obtain catalyst microspheres. The catalyst microspheres were calcined at 500°C for 1 h, washed twice, each time with 8 times the dry weight of the catalyst microspheres of deionized water, and dried at 120°C for 2 h, to obtain a catalytic cracking catalyst D-1. The catalyst composition and properties are shown in Table 2.

[0123] Table 2 Dry basis composition and properties of the catalysts

[0124]

[0125]

[0126] Note: In Table 2, the contents of the aluminum sol and the pseudo-boehmite are based on aluminum oxide; the micro- reaction activity in Table 2 is the micro- reaction activity measured according to Test Example 1, except that the time for the water vapor aging inactivation treatment is different.

[0127] Test Example 1

[0128] This test example is used to evaluate the performance of the catalytic cracking catalysts provided above.

[0129] The catalysts above were subjected to a 800°C, 100% water vapor aging inactivation treatment for 17 h. The catalyst loading was 9 g, and the reaction raw material was a Wuhan mixed three raw oil, the raw material of which is shown in Table 3. The reaction temperature was 500°C, and the catalyst to oil ratio (by weight) was 6. The measured catalyst performance parameters are shown in Table 4.

[0130] wherein the conversion rate = gasoline yield + liquefied gas yield + dry gas yield + coke yield;

[0131] Light oil yield = gasoline yield + diesel yield;

[0132] Liquid yield = LPG yield + gasoline yield + diesel yield;

[0133] Coke selectivity = coke yield / conversion;

[0134]

[0135] Table 3

[0136]

[0137]

[0138] Table 4

[0139]

[0140] As can be seen from Table 4, the catalytic cracking catalyst prepared by the method provided by the present application has better and more excellent heavy oil cracking performance, higher conversion rate, gasoline yield and liquid yield, and lower heavy oil yield and diesel yield than the catalytic cracking catalyst prepared by the prior art. As can be seen from Example 2 in which the content of the molecular sieve is lower, the prepared catalyst C-2 still has better and more excellent heavy oil cracking performance and higher conversion rate and gasoline yield than Comparative Example 1. Meanwhile, the catalyst manufacturing cost is reduced.

[0141] Example 5

[0142] This example is used to illustrate the preparation of the gelatinous residue and the catalytic cracking catalyst.

[0143] Preparation of the gelatinous residue:

[0144] (1) The wet gelatinous residue C (gelatinous liquid, composition see Table 5 below) obtained in the catalyst preparation process and the molecular sieve modification process is conveyed by an axial screw to a thin film dryer, the thin film dryer uses water vapor to heat the material, the water vapor temperature is 160°C, the outlet temperature is 120°C, and the solid content of the dried material is 60%;

[0145] (2) The material obtained in step (1) is beaten to a solid content of 30%, (NH4)2SO4 and 15% mass concentration hydrochloric acid are added to the slurry: the mass ratio of (NH4)2SO4 and 15% mass concentration hydrochloric acid is 2:1, after 1 hour of exchange, the material is filtered by a belt filter, the filter cake is beaten with deionized water to a solid content of 30%;

[0146] (3) The slurry material after washing in step (2) is ground in a ball mill for 8 hours, and finally a glue residue product D is obtained, whose composition and properties are shown in Table 5 below.

[0147] Preparation of the catalytic cracking catalyst:

[0148] In a reaction kettle, aluminum sol is added according to the proportions in Table 6 and stirred, pseudo-boehmite is added, deionized water (also referred to as acidic water in the present application) is added and stirred for 40 min, glue residue product D is added and stirred for 60 min, then 22 wt% hydrochloric acid (the weight ratio of hydrochloric acid to pseudo-boehmite is 0.1) is added and stirred for 30 min, and finally HRY-2 molecular sieve (solid content 80 wt%, rare earth content 17 wt%) slurry is added and stirred for 30 min, to obtain a catalyst slurry (solid content 34%). The catalyst slurry is spray dried to obtain catalyst microspheres. The obtained catalyst microspheres are calcined at 500°C for 1 h, washed twice, each time using 8 times the dry weight of the catalyst microspheres of deionized water for washing, and dried at 120°C for 2 hours, to obtain a catalytic cracking catalyst C-5. The composition and properties of the catalyst are shown in Table 6.

[0149] Example 6

[0150] This example is used to illustrate the preparation of glue residue and catalytic cracking catalyst.

[0151] The glue residue is prepared according to the method of Example 5. A catalytic cracking catalyst is prepared according to the proportions in Table 6 and the process of Example 5, to obtain C-6. The composition and properties of the catalyst are shown in Table 6.

[0152] Comparative Example 2

[0153] The wet glue residue C obtained in the catalyst preparation process and molecular sieve modification process is calcined at 500°C for 2 h, then ground to obtain glue residue E, whose composition is shown in Table 5 below. A catalytic cracking catalyst is prepared according to the proportions in Table 6 and the process of Example 5, except that the catalyst washing process is washed four times, the first two times each using 8 times the dry weight of the catalyst microspheres of deionized water for washing, and adding 2% ammonium sulfate based on the dry weight of the catalyst microspheres, and the last two times each using 8 times the dry weight of the catalyst microspheres of deionized water for washing, and dried at 120°C for 2 hours, to obtain D-2. The composition and properties of the catalyst are shown in Table 6.

[0154] Comparative Example 3

[0155] The wet carbonaceous sludge C is treated according to the method of patent CN1150301C, dried at 150℃ / 2h, 5% ammonium sulfate is added, the water-to-sludge ratio is 5:1, the pH value is adjusted to less than 3.5 with hydrochloric acid, hot water exchange is performed for 30min, and then filtration or sedimentation is performed, and the supernatant is discarded; 5% ammonium sulfate is added, the water-to-sludge ratio is 5:1, the pH value is adjusted to less than 3.5 with hydrochloric acid, hot water exchange is performed for 30min, and then filtration or sedimentation is performed, and then the sludge is dried and calcined at 500℃ / 2h to obtain carbonaceous sludge F, the composition of which is shown in Table 5 below, and the catalytic cracking catalyst is prepared according to the proportioning of Table 6 and the process of Example 5 to obtain D-3. The catalyst composition and properties are shown in Table 6.

[0156] Table 5 Dry basis composition and properties of carbonaceous sludge before and after treatment

[0157]

[0158] Table 6 Dry basis composition and properties of the catalyst

[0159]

[0160]

[0161] Note: In Table 6, the contents of aluminum sol and pseudoboehmite are calculated as aluminum oxide; in Table 6, the micro-reaction activity is the micro-reaction activity measured according to Test Example 1, except that the time for water vapor aging and deactivation treatment is different.

[0162] Test Example 2

[0163] This test example is used to evaluate the performance of the catalytic cracking catalyst provided above.

[0164] The performance of the catalysts provided in the above examples and comparative examples is evaluated according to the conditions of Test Example 1 described above, and the results are shown in Table 7.

[0165] Table 7

[0166]

[0167] As can be seen from Table 7, the catalytic cracking catalyst C-5 prepared by replacing the molecular sieve with the carbonaceous sludge prepared by the method provided by the present application has equivalent or higher heavy oil cracking performance, light oil yield and liquid yield compared with the catalytic cracking catalyst D-3 prepared by the prior art. Although the catalytic cracking catalyst C-5 has equivalent heavy oil cracking performance compared with the catalytic cracking catalyst D-2, the carbonaceous sludge of D-2 is sticky and hardens, the carbonaceous sludge cannot be continuously fed, the hardened material cannot be pulped and ground after calcination, the catalyst wear index cannot be guaranteed, the manufacturing cost is high, and industrialization cannot be realized.

[0168] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including that each technical feature is combined in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A method for treating adhesive liquid, characterized in that, The method includes the following steps: (1) Break up the adhesive; (2) Pulp the material obtained in step (1) and then wash it; (3) The material obtained after washing is ground, and the grinding process yields particles with a DV (0.5) of no more than 6 micrometers and a DV (0.9) of no more than 10 micrometers; The breaking of the glue in step (1) is carried out in accordance with step (1-1) and / or step (1-2); Step (1-1) includes drying the adhesive solution at a low temperature, wherein the conditions for low-temperature drying include: the temperature of the drying medium is 100-250°C and the outlet temperature is 60-120°C; Step (1-2) includes pulping the adhesive to obtain a slurry with a solid content of 10-20% by weight, and drying the slurry at a high temperature, wherein the temperature of the high-temperature drying medium is above 300°C. Based on the total dry basis of the adhesive solution, the adhesive solution comprises: 20-40% by weight of Al2O3, 30-65% by weight of SiO2, 10-25% by weight of Re2O3, and 2-10% by weight of Na2O. The adhesive solution includes adhesive solutions obtained from the preparation process of catalytic cracking catalyst and / or the molecular sieve modification process; The washing medium used in step (2) is selected from at least one of ammonium sulfate, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and citric acid.

2. The processing method according to claim 1, wherein, Based on the total dry basis of the adhesive, the adhesive further includes: 1-10% by weight of SO4. 2- 0.5-2% by weight of Fe2O3 and 1-3% by weight of Cl - .

3. The processing method according to claim 1, wherein, The solid content of the adhesive solution is 10-25% by weight. And / or, the crystallinity of the adhesive solution is above 10%.

4. The processing method according to claim 3, wherein, The solid content of the adhesive solution is 15-20% by weight. And / or, the crystallinity of the adhesive solution is 10-25%.

5. The processing method according to any one of claims 1-4, wherein, The solid content of the material obtained by low-temperature drying in step (1-1) is 30-70% by weight.

6. The processing method according to claim 5, wherein, The solid content of the material obtained by low-temperature drying in step (1-1) is 50-70% by weight.

7. The processing method according to any one of claims 1-4, wherein, The conditions for low-temperature drying in step (1-1) include: the temperature of the drying medium is 120-160℃, and the outlet temperature is 80-120℃.

8. The processing method according to any one of claims 1-4, wherein, The low-temperature drying in step (1-1) employs at least one of steam drying, microwave drying, and film drying.

9. The processing method according to any one of claims 1-4, wherein, The solid content of the pulp obtained from step (1-2) is 12-16% by weight. And / or, the temperature of the high-temperature drying medium is above 500°C; And / or, the outlet temperature of the high-temperature dryer is 150-180°C.

10. The processing method according to any one of claims 1-4, wherein, The temperature of the high-temperature drying medium is 500-600℃.

11. The processing method according to any one of claims 1-4, wherein, The high-temperature drying process employs flash drying.

12. The processing method according to any one of claims 1-4, wherein, The solid content of the material obtained by high-temperature drying is 30-70% by weight.

13. The processing method according to any one of claims 1-4, wherein, The solid content of the material obtained by high-temperature drying is 50-70% by weight.

14. The processing method according to any one of claims 1-4, wherein, In step (2), deionized and deionized water is used for pulping.

15. The processing method according to any one of claims 1-4, wherein, The solid content of the slurry obtained by pulping in step (2) is 25-60% by weight.

16. The processing method according to claim 15, wherein, The solid content of the slurry obtained by pulping in step (2) is 25-35% by weight.

17. The processing method according to any one of claims 1-4, wherein, The washing medium used in step (2) is ammonium sulfate and hydrochloric acid, with a mass ratio of 1-3:

1.

18. The processing method according to any one of claims 1-4, wherein, The washing in step (2) results in a product in which the content of sodium oxide is not higher than 2.5% by weight and the content of magnesium oxide and calcium oxide is not higher than 0.5% by weight, based on the total dry weight.

19. The processing method according to any one of claims 1-4, wherein, The grinding process described in step (3) is carried out in a shearing machine, ball mill, or sand mill.

20. The resin residue obtained by the processing method according to any one of claims 1-19, wherein the resin residue comprises, based on the total dry weight, the resin residue as: 15-30 wt% Al2O3, 30-50 wt% SiO2, 5-15 wt% Re2O3, 0.1-2 wt% Na2O, 1-10 wt% SO4 2- 1-2% by weight Fe2O3 and 1-5% by weight Cl - .

21. The adhesive residue according to claim 20, wherein, The crystallinity of the resin residue is above 10%.

22. The adhesive residue according to claim 21, wherein, The crystallinity of the resin residue is 10-25%.

23. The adhesive residue according to claim 20, wherein, The specific surface area of ​​the resin residue is 200 m². 2 / g or more.

24. The adhesive residue according to any one of claims 20-23, wherein, The particle size DV (0.5) of the glue residue is no greater than 6 micrometers, and the particle size DV (0.9) is no greater than 10 micrometers.

25. A method for preparing a catalytic cracking catalyst, the method comprising: A catalyst slurry is prepared by pulping a binder, a molecular sieve, and the adhesive residue as described in any one of claims 20-24, and optionally clay, and the catalyst slurry is then spray-dried and optionally calcined.

26. The preparation method according to claim 25, wherein, The binder is selected from at least one of boehmite, aluminum sol, silica sol, magnesium aluminum sol, zircon sol, and titanium sol.

27. The preparation method according to claim 25, wherein, The binder is boehmite and alumina sol.

28. The preparation method according to claim 25, wherein, The clay is at least one of the following: kaolin, hydrous kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, rettosite, sepiolite, attapulgite, hydrotalcite, and bentonite.

29. The preparation method according to claim 28, wherein, The clay is kaolin and / or halloysite.

30. The preparation method according to claim 25, wherein, The molecular sieve is at least one of Y zeolite, ZSM-5 zeolite, and β-type zeolite.

31. The preparation method according to any one of claims 25-30, wherein, The amounts of binder, molecular sieve, slag, and clay used in the prepared catalytic cracking catalyst are such that, based on the dry weight of the catalytic cracking catalyst, the molecular sieve content is 20-35% by weight; the clay content is 0-50% by weight; the binder content is 5-30% by weight (based on oxides); and the slag content is 2-50% by weight (based on dry weight).

32. The preparation method according to claim 31, wherein, The amounts of binder, molecular sieve, slag, and clay used in the prepared catalytic cracking catalyst are such that, based on the dry weight of the catalytic cracking catalyst, the molecular sieve content is 20-30% by weight; the clay content is 20-40% by weight; the binder content is 10-20% by weight (based on oxides); and the slag content is 5-25% by weight (based on dry weight).

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