CN114425413B - Catalytic cracking auxiliary agent for increasing concentration of butene in liquefied gas and preparation method and application thereof - Google Patents

Catalytic cracking auxiliary agent for increasing concentration of butene in liquefied gas and preparation method and application thereof Download PDF

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CN114425413B
CN114425413B CN202010998197.8A CN202010998197A CN114425413B CN 114425413 B CN114425413 B CN 114425413B CN 202010998197 A CN202010998197 A CN 202010998197A CN 114425413 B CN114425413 B CN 114425413B
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catalytic cracking
modified
acid
residue
mixing
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CN114425413A (en
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于善青
严加松
张杰潇
凤孟龙
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/36—Rhenium
    • 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
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a catalytic cracking auxiliary agent for improving the concentration of butene in liquefied gas, a preparation method and application thereof, wherein the catalytic cracking auxiliary agent comprises 10-50 wt% of beta zeolite, 5-35 wt% of modified sol, 2-30 wt% of modified gumming residue and 10-70 wt% of clay based on the total weight of the catalytic cracking auxiliary agent; based on the total weight of the modified adhesive residue, the modified adhesive residue contains 0 to 2.0 weight percent of Na 2 O, 10-40 wt% of Al 2 O 3 20 to 70 weight percent of SiO 2 And 1 to 15 wt.% RE 2 O 3 The specific surface area of the modified adhesive slag is 180-350 m 2 Per gram, the pore volume is 0.6-1.0 mL/g, and the average pore diameter is 10-50 nm. The catalytic cracking catalyst has higher cracking capacity and can effectively improve the concentration of butene in liquefied gas.

Description

Catalytic cracking auxiliary agent for increasing concentration of butene in liquefied gas and preparation method and application thereof
Technical Field
The invention relates to a catalytic cracking auxiliary agent for increasing the concentration of butene in liquefied gas, a preparation method and application thereof.
Background
With the enhancement of environmental awareness, the quality standard of the automotive gasoline is continuously updated. The new standard of motor gasoline and GB17930-2016 clearly specify that national VI standard gasoline is implemented in stages from 2019, and compared with national V standard, the benzene, aromatic hydrocarbon and olefin contents of gasoline under the national VI standard are reduced, so that the gasoline blending component scheme in China is difficult to meet the requirements. Because the alkylation gasoline has high octane number and zero content of olefin, aromatic hydrocarbon and benzene, compared with the traditional catalytic gasoline and reforming gasoline under the national VI standard, the alkylation gasoline is a good gasoline blending component, and the proportion of the alkylation gasoline in the gasoline blending component can be greatly improved. The main feeds to the alkylation unit are isobutane and butenes. Nearly 70% of the butenes worldwide come from catalytic crackers and the technology for producing butene fractions from catalytic crackers has the advantage of low investment and cost, with many companies trying to obtain greater butene yields from the catalytic cracking process.
Beta zeolite has both acid catalytic property and structural selectivity due to its structural specificity, and has been rapidly developed into a novel catalytic material in recent years. The use of zeolite beta in catalytic cracking catalysts to produce lower olefins has also been reported. U.S. patent No. 4837396 discloses a catalyst containing zeolite beta and zeolite Y, which contains a metal ionic compound as a stabilizer to improve the hydrothermal stability and mechanical strength of the catalyst. The stabilizer can directly act with beta zeolite or be introduced in the preparation process. CN1055105C discloses a cracking catalyst for producing isobutene and isoamylene, which contains phosphorus and rare earth, five-membered ring high-silicon zeolite 6-30 wt%, USY zeolite 5-20 wt%, beta zeolite 1-5 wt%, clay 30-60 wt% and inorganic oxide 15-30 wt%, and the catalyst has the characteristics of producing isobutene and isoamylene under the technological conditions of catalytic cracking, and can co-produce high-octane gasoline. CN104998681a discloses a catalytic cracking aid for increasing the concentration of low-carbon olefins and a method for preparing the same, the aid comprising a boron-modified phosphorus and metal-containing beta molecular sieve, an inorganic oxide binder, a group VIII metal additive, a phosphorus additive, and optionally clay. The catalytic cracking auxiliary agent is applied to the catalytic cracking of petroleum hydrocarbon, can increase the concentration of isobutene in catalytic cracking liquefied gas, and reduces the yield of coke.
The active component of the catalyst is of fundamental importance, but the role of the matrix is not neglected. It is generally believed that the catalyst matrix should have a relatively large pore size, suitable activity and good hydrothermal stability so that the catalyst can withstand the harsh hydrothermal operating conditions and pre-crack the heavy feedstock.
The gum residue is produced by the operations of sedimentation, filtration, residue cutting and the like of waste water generated in the production of the catalytic cracking catalyst, and Al is used 2 O 3 And SiO 2 The waste residue as main component also contains 2 to 15 percent of Na 2 O and 1-15% RE 2 O 3 . At present, a plurality of catalyst manufacturers generally discard the glue residues directly and do not reuse the glue residues, so that a large amount of resources such as Si, al and the like are lost and wasted. Meanwhile, the waste and landfill of the gumming residues occupies a large amount of land resources, the gumming residues enter the soil and enter the water along with natural circulation, so that the pollution of the soil and the water resources is caused, and serious environmental problems are caused. If the technology route of industrial feasibility and cost economy is adopted for utilization, the environmental protection treatment pressure of enterprises can be reduced, the production cost of the enterprises can be reduced, and the economic benefit can be improved.
CN104261425a relates to a method for efficiently utilizing the glue residue of catalytic cracking catalyst, which comprises the steps of firstly activating the glue residue, and then synthesizing the superfine Y-type molecular sieve by utilizing a hydrothermal crystallization method under the action of a structure directing agent. The structural parameters such as the crystal structure, the specific surface, the granularity and the like of the obtained molecular sieve can be conveniently modulated by regulating and controlling the synthesis condition of the molecular sieve and the pretreatment condition of the gumming residue; the obtained product has high specific surface and stable structure.
Disclosure of Invention
The invention aims to provide a catalytic cracking auxiliary agent for increasing the concentration of butene in liquefied gas, and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a catalytic cracking aid for increasing the concentration of butene in liquefied gas, the catalytic cracking aid comprising 10 to 50 wt% of beta zeolite, 5 to 40 wt% of modified sol, 2 to 30 wt% of modified cement and 10 to 70 wt% of clay, based on the total weight of the catalytic cracking aid;
in the way describedThe total weight of the modified adhesive residue is taken as the reference, and the modified adhesive residue contains 0 to 2.0 weight percent of Na 2 O, 10-40 wt% of Al 2 O 3 20 to 70 weight percent of SiO 2 And 1 to 15 wt.% RE 2 O 3 The specific surface area of the modified glue residue is 180-350 m 2 Per gram, the pore volume is 0.6-1.0 mL/g, and the average pore diameter is 10-50 nm;
the modified sol contains 20 to 50 wt% of Al based on the total weight of the modified sol 2 O 3 And 50 to 80 wt.% P 2 O 5 The molar ratio of P to Al is 1.5-2.5, the pH value of the modified sol is 1.5-3.5, and the average colloidal particle diameter is 10-50 nm.
Optionally, the catalytic cracking auxiliary agent contains 10-40 wt% of beta zeolite, 5-35 wt% of modified sol, 2-20 wt% of modified gummy residue and 20-60 wt% of clay.
In a second aspect, the present invention provides a method for preparing the catalytic cracking aid provided in the first aspect, the method comprising: mixing beta zeolite, modified sol, modified glue residue, a first solvent and clay, and then performing first drying and roasting;
wherein, the modified rubber residue is prepared by the following steps: mixing the solid gum residue, the second solvent and the acid solution, reacting the obtained slurry at 20-90 ℃ for 30-120 min, and taking out the solid, wherein the pH value of the slurry is 1-5.
Optionally, the method for preparing the catalytic cracking catalyst comprises the following steps: mixing and pulping the clay, the modified gumming residue and the solvent to obtain first slurry; and mixing the first slurry, the beta zeolite and the modified sol, and then performing first drying and roasting on the obtained second slurry.
Optionally, the method for preparing the solid gum residue comprises the following steps: performing secondary drying on the glue residue to obtain the solid glue residue;
the solid gum residue has a solid content of 70-95 wt%; based on the dry weight of the solid gum residue, the solid gum residue contains 2 to 15 weight percent of Na 2 O, 10-50 wt% of Al 2 O 3 30 to 70 weight percent of SiO 2 And 1 to 15 wt.% RE 2 O 3 。
Optionally, the modified sol is prepared by a method comprising the following steps:
mixing an aluminum source, water and an organic solvent to obtain a first mixture, mixing the first mixture with phosphoric acid to obtain a second mixture, and reacting the second mixture at 40-65 ℃ for 30-180 min.
Optionally, mixing the first mixture with phosphoric acid comprises:
mixing and stirring the first mixture and the first part of phosphoric acid at 40-65 ℃ for 10-60 min to obtain a third mixture; mixing the third mixture with a second portion of the phosphoric acid to obtain the second mixture.
Optionally, the weight of the first portion of phosphoric acid is 30 to 70% based on the total weight of the first and second portions of phosphoric acid.
Optionally, the organic solvent is selected from one or more of methanol, ethanol, isopropanol, n-butanol, isobutanol, heptane, n-hexane, cyclohexane, n-octane, acetone, butanone, formic acid, oxalic acid, acetic acid and propionic acid; the weight of the organic solvent is 2-10% of the weight of the aluminum source, and the weight of the aluminum source is calculated as aluminum oxide.
Optionally, the beta zeolite is selected from H beta zeolite and/or modified beta zeolite, wherein the modified beta zeolite contains one or more of phosphorus, iron and rare earth metals;
the clay is one or more selected from kaolin, rectorite, diatomite, montmorillonite, bentonite and sepiolite;
the acid solution contains organic acid and/or inorganic acid, wherein the organic acid is one or more selected from oxalic acid, acetic acid and citric acid, and the inorganic acid is one or more selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, ammonium sulfate and ammonium chloride;
the first solvent and the second solvent are each independently selected from one or more of deionized water, decationized water and distilled water.
The third aspect of the invention provides an application of the catalytic cracking auxiliary agent provided by the first aspect of the invention in catalytic cracking of crude oil.
Optionally, the conditions for catalytic cracking of the crude oil include: the temperature is 490-530 ℃, the time is 1-3s, and the catalyst-oil ratio is 3-8;
the content of the catalytic cracking auxiliary agent is 1-50 wt% based on the total weight of the catalytic cracking auxiliary agent and the catalytic cracking catalyst.
Through the technical scheme, the catalytic cracking auxiliary agent contains modified rubber residues, can realize recycling of resources such as silicon, aluminum, rare earth and the like, and is beneficial to improving the cracking activity of the catalytic cracking auxiliary agent and the concentration of butene in liquefied gas.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the invention provides a catalytic cracking auxiliary agent for increasing the concentration of butene in liquefied gas, which comprises 10-50 wt% of beta zeolite, 5-40 wt% of modified sol, 2-30 wt% of modified gumming residue and 10-70 wt% of clay based on the total weight of the catalytic cracking auxiliary agent;
based on the total weight of the modified adhesive residue, the modified adhesive residue contains 0 to 2.0 weight percent of Na 2 O, 10-40 wt% of Al 2 O 3 20 to 70 weight percent of SiO 2 And 1 to 15 wt.% RE 2 O 3 The specific surface area of the modified adhesive slag is 180-350 m 2 Per gram, the pore volume is 0.6-1.0 mL/g, and the average pore diameter is 10-50 nm;
the modified sol contains 20 to 50 wt% of Al based on the total weight of the modified sol 2 O 3 And 50 to 80 wt.% P 2 O 5 The molar ratio of P to Al is 1.5 to the whole2.5, the pH value of the modified sol is 1.5-3.5, and the average colloidal particle diameter is 10-50 nm.
Wherein RE 2 O 3 Refers to rare earth metal oxides, which are well known to those skilled in the art and are not described in detail herein. The catalytic cracking additive contains modified gumming residues, realizes effective recycling of silicon, aluminum, rare earth and other resources in the production process of the catalyst, has higher cracking activity, and can obviously increase the concentration of butene in liquefied gas.
According to the invention, the modified sol may contain 25 to 40 wt% of Al, based on the total weight of the modified sol 2 O 3 And 60 to 75 wt.% P 2 O 5 The molar ratio of P to Al is 1.8-2.2, the pH value of the modified sol is 2.0-3.0, and the average colloidal particle diameter is 20-30 nm. The catalytic cracking auxiliary agent adopts the modified sol as the binder, has proper average colloidal particle diameter range, forms a handle annular system among colloidal particles, and can reduce aggregation among colloidal particles to form large particles with the diameter of 50-100 nm. Compared with the conventional aluminum phosphate sol, the aluminum phosphate colloid system is more stable, ensures that the catalytic cracking auxiliary agent has good abrasion resistance and also has higher specific surface area, crystallinity and cracking activity.
According to the present invention, the catalytic cracking aid may contain 10 to 40 wt% of beta zeolite, 5 to 35 wt% of modified sol, 2 to 20 wt% of modified cement and 20 to 60 wt% of clay.
According to the invention, the specific surface area of the catalytic cracking auxiliary can be 200-300 m 2 The water drop pore volume per gram can be 0.35-0.45 mL/g, the abrasion index can be 0.5-3.0%, and the micro-inverse activity index can be 40-60.
In a second aspect, the present invention provides a method for preparing the catalytic cracking aid provided in the first aspect, the method comprising: mixing beta zeolite, modified sol, modified glue residue, a first solvent and clay, and then performing first drying and roasting;
wherein, the modified glue residue is prepared by the following steps: mixing the solid gum residue, the second solvent and the acid solution, reacting the obtained slurry at 20-90 ℃ for 30-120 min, and taking out the solid, wherein the pH value of the slurry is 1-5, and the pH value is preferably 2-4.
The method can realize recycling of the gumming residues, and can prepare the catalytic cracking auxiliary agent with good cracking activity.
In one embodiment, the modified cement is prepared by a method comprising the steps of: the solid gum residue and the second solvent are mixed according to the weight ratio of 1: (5-20), mixing the obtained mixture with an acid solution to obtain slurry, reacting the obtained slurry at 20-90 ℃ for 30-120 min, taking out solid, and drying the solid at 60-150 ℃ for 2-12 hours.
According to the present invention, the first drying mode is not particularly limited, and may be, for example, spray drying, constant temperature drying, air flow drying, and the tail gas temperature of spray drying may be 130 to 200 ℃, preferably 140 to 180 ℃. The calcination is well known to those skilled in the art, and may be performed in, for example, a muffle furnace or a tube furnace, the temperature of the calcination may be varied within a wide range, preferably 300 to 650 ℃, and the time may be 1 to 5 hours, and the calcination atmosphere is not particularly limited, and may be an air atmosphere or an inert atmosphere, and inert gases may include helium, argon, and the like.
In one embodiment of the present invention, a method of preparing a catalytic cracking catalyst comprises: mixing clay, modified gumming slag and solvent, and pulping to obtain first slurry; after the first slurry, beta zeolite and modified sol are mixed, the obtained second slurry is subjected to first drying and calcination. The time of mixing and beating is not particularly limited, and may be, for example, 30 to 120 minutes. More preferably, the first slurry and the modified sol are mixed and stirred for 10 to 90 minutes, and then the beta zeolite is added and mixed and stirred for 10 to 60 minutes.
According to the invention, na of the modified gum residue 2 The O content may be 0 to 1.5 wt.%.
In one embodiment of the inventionIn an embodiment, a method of preparing solid gum residue may include: performing secondary drying on the glue residue to obtain solid glue residue; the water content of the solid gum residue is 2-20 wt%. The second drying method is not particularly limited, and may be spray drying, air drying, constant temperature drying, preferably spray drying, and the spray drying tail gas temperature is 130 to 200 ℃, more preferably 140 to 180 ℃. The method of the invention uses the glue residue after drying and molding, and can solve the problems of high viscosity and Na of the glue residue 2 The problems of difficult O washing and difficult filtration are beneficial to preparing the catalytic cracking auxiliary agent with good cracking activity.
According to the invention, the solid content of the solid gum residue is 70-95 wt%, and the solid gum residue contains 2-15 wt% of Na based on the dry weight of the solid gum residue 2 O, 10-50 wt% of Al 2 O 3 30 to 70 weight percent of SiO 2 And 1 to 20 wt%, e.g., 1 to 15 wt% RE 2 O 3 。
According to the invention, the modified sol can be prepared by a method comprising the following steps: mixing an aluminum source, water and an organic solvent to obtain a first mixture, mixing the first mixture with phosphoric acid to obtain a second mixture, and reacting the second mixture at 40-65 ℃ for 30-180 min. The temperature of the mixing is not particularly limited, and may be 0 to 40 ℃. The concentration of phosphoric acid may vary widely and is preferably 60 to 98% by weight. According to the method, the organic solvent is added before the peptization aluminum phosphate source is added, so that the stability and fluidity of sol-gel groups can be improved, and the preparation of the catalytic cracking auxiliary agent with better cracking activity is facilitated.
In one embodiment of the invention, mixing the first mixture with phosphoric acid comprises: mixing and stirring the first mixture and the first part of phosphoric acid at 40-65 ℃ for 10-60 min to obtain a third mixture; the third mixture is mixed with a second portion of the phosphoric acid to yield a second mixture.
According to the invention, the weight of the first part of phosphoric acid may be 30 to 70%, preferably 30 to 60%, based on the total weight of the first and second parts of phosphoric acid.
The solids content of the modified sol according to the invention may vary within wide limits, preferably from 25 to 50% by weight, more preferably from 25 to 45% by weight.
According to the present invention, the organic solvent may be one or more selected from methanol, ethanol, isopropanol, n-butanol, isobutanol, heptane, n-hexane, cyclohexane, n-octane, acetone, butanone, formic acid, oxalic acid, acetic acid and propionic acid; the weight of the organic solvent is 2-10% of the weight of the aluminum source, and the weight of the aluminum source is calculated by alumina.
According to the invention, the beta zeolite may be selected from H beta zeolite and/or modified beta zeolite, wherein the modified beta zeolite contains one or more of phosphorus, iron and rare earth metals; the rare earth metal may be Sc, Y, la, ce, pr or the like. Clays are well known to those skilled in the art and may be selected from one or more of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite and sepiolite. The acid solution may contain an organic acid selected from one or more of oxalic acid, acetic acid and citric acid, and/or an inorganic acid selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, ammonium sulfate and ammonium chloride. The first solvent and the second solvent may each be independently selected from one or more of deionized water, decationized water, and distilled water.
The third aspect of the invention provides an application of the catalytic cracking auxiliary agent provided by the first aspect of the invention in catalytic cracking of crude oil.
According to the present invention, when the catalytic cracking aid of the present invention is used in the catalytic cracking process, the catalytic cracking aid may be added to the catalytic cracking reactor alone or may be used in combination with a catalytic cracking catalyst. In one embodiment, the catalytic cracking aid is provided in an amount of 1 to 50 wt%, preferably 5 to 30 wt%, based on the total amount of catalytic cracking aid and cracking catalyst.
According to the present invention, the conditions for catalytic cracking of crude oil may include: the temperature is 490-530 ℃, the time is 1-3s, and the agent-oil ratio is 3-8.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The gum residue is obtained from waste water generated in the catalytic cracking catalyst production by sedimentation, filtration, residue cutting and other operations, the solid content of the gum residue is 25 wt%, and the gum residue contains 9.0 wt% of Na based on the dry weight of the gum residue 2 O, 23.0 wt% Al 2 O 3 48.0 wt% SiO 2 9.2 wt% RE 2 O 3 ；
Kaolin is produced by the company su zhou kaolin with a solids content of 76% by weight;
pseudo-boehmite produced by Shandong Albazaar with a solids content of 62.0 wt%;
the alumina content in the alumina sol was 21.5 wt%; the solid content of the aluminum phosphate sol is 28.0 weight percent and contains P 2 O 5 75%;
hydrochloric acid is produced by Beijing chemical plant, the specification is analytically pure, and the mass concentration is 36%;
phosphoric acid is produced by Beijing chemical plant, the specification is analytically pure, and the mass concentration is 85%;
solid content of H beta zeolite 75 wt%, siO 2 /Al 2 O 3 ＝25，Na 2 The O content was 0.15 wt%;
the H beta zeolite is produced by China petrochemical catalyst, and the rest of reagents are produced by China medicine group chemical reagent, and the specifications are all analytically pure;
the sample was 1.33X10 by using ASAP 2405N V1.01 automatic adsorbent, low temperature static nitrogen adsorption capacity method of Micromerics company -2 Vacuum degassing at 300 deg.C under Pa for 4 hr, and mixing with N 2 The adsorption-desorption isotherms of the samples were determined at 77.4K for the adsorption media. Calculating the specific surface area of the sample according to the BET formula (S BET ) Determination of the relative pressure p/p 0 Sample adsorption N when=0.98 2 Converting the volume of the liquid nitrogen into a liquid nitrogen volume, namely a pore volume;
microreaction Activity index: the micro-reactive activity of the light oil of the sample is evaluated by adopting a standard method of RIPP92-90 (see the method of petrochemical analysis (the method of RIPP test) Yang Cuiding, et al, scientific press, published 1990), the catalyst loading is 5.0g, the reaction temperature is 460 ℃, the raw oil is straight-run light diesel oil with the distillation range of 235-337 ℃, the product composition is analyzed by gas chromatography, and the micro-reactive activity of the light oil is calculated according to the product composition. Micro-reactivity index= (gasoline yield + gas yield + coke yield below 216 ℃ in the product)/total feed x 100%;
determining the average pore diameter of the sample by adopting a Q/SH 3360-206 method;
determining the average colloidal particle diameter of the sample by using a TEM method;
the sample composition was determined using X-ray fluorescence spectroscopy (XRF).
Example 1
(1) Preparation of modified sol: mixing 52.2g of pseudo-boehmite, 0.65g of ethanol and 149g of deionized water, pulping for 30min, and uniformly dispersing to obtain a first mixture; then pouring 60g of 85 wt% phosphoric acid solution, continuously stirring for 30min at 18 ℃, adding the rest 50g of 85 wt% phosphoric acid solution to obtain a second mixture, heating the second mixture to 45 ℃, and stirring for 180min; a modified sol PA-1 having a solids content of 32% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 32.3%, P 2 O 5 The mass content is 67.2%, the P/Al molar ratio is 1.5, the pH value is 3.3, and the average colloidal particle diameter is 30nm.
(2) Preparing modified glue residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 25 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 180 ℃ to obtain solid gumming slag (the solid content is 92 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:10, adding hydrochloric acid with the concentration of 36 weight percent to adjust the pH value of the slurry to 3.0, stirring for 90min at 60 ℃, filtering to obtain solid, and then drying at 120 ℃; and mixing the solid obtained by drying with deionized water according to a mass ratio of 1:10, adding hydrochloric acid with the concentration of 36 weight percent to adjust the pH value of the slurry to 3.0, stirring for 90min at 60 ℃, filtering to obtain solid, and then drying again at 120 ℃, wherein the obtained modified glue residue is JZ-1. Analyzed, na of 2 The content of O was 1.15 wt%, A1 2 O 3 The content of (C) was 27.7 wt%, siO 2 The content of (C) was 59.9 wt%, RE 2 O 3 The content of (C) was 8.3% by weight and the specific surface area was 220m 2 Per g, pore volume 0.65mL/g, average pore diameter 35nm.
(3) Preparation of catalytic cracking auxiliary agent: 79g of kaolin, 20g of the modified cement residue (JZ-1) and 451g of decationized water are added into a pulping tank for pulping for 60min, 93g of H beta zeolite is added, stirring is carried out for 30min, 156g of the modified sol (PA-1) is finally added, the obtained slurry is subjected to homogeneous dispersion (stirring) for 30min, the solid content of the obtained slurry is 25 wt%, then the obtained slurry is subjected to spray drying and shaping, and roasting is carried out at 500 ℃ for 2H, so that the catalytic cracking auxiliary CB-1 provided by the invention is obtained, and the composition and characteristic parameters are shown in table 1 and are the same in the following examples.
Example 2
(1) Preparation of modified sol: 41g of pseudo-boehmite, 2.55g of normal hexane and 168g of deionized water are mixed and pulped for 60min, and the mixture is uniformly dispersed to obtain a first mixture; then pouring 60g of 85 wt% phosphoric acid solution, continuously stirring for 20min at 18 ℃, adding the rest 60g of 85 wt% phosphoric acid solution to obtain a second mixture, heating the second mixture to 65 ℃, and stirring for 60min; a modified sol PA-2 having a solids content of 30% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 25.5%, P 2 O 5 The mass content is 74.5%, the P/Al molar ratio is 2.1, the pH value is 2.8, and the average colloidal particle diameter is 30nm.
(2) Preparing modified glue residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 20 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 150 ℃ to obtain solid gumming slag (the solid content is 88 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:8, adding 30 weight percent nitric acid to adjust the pH value of the slurry to 3.5, stirring for 60min at 90 ℃, filtering to obtain solid, and then drying at 120 ℃; and mixing the solid obtained by drying with deionized water according to a mass ratio of 1:8 mixing, adding 30 wt% nitric acid to adjust pH to 3.5, stirring at 90deg.C for 60min, filtering to obtain solid, drying again at 120deg.C to obtain modified gum residue, designated JZ-2, and analyzing to obtain Na 2 O content was 0.56 wt%, A1 2 O 3 Is 22.6 wt%，SiO 2 The content of (C) was 69.7 wt%, RE 2 O 3 The content of (C) was 8.2% by weight, and the specific surface area was 210m 2 Per g, pore volume was 0.72mL/g and average pore diameter was 30nm.
(3) Preparation of catalytic cracking auxiliary agent: 79g of kaolin, 30g of the modified cement residue (JZ-2) and 444g of decationized water are added into a pulping tank for pulping for 60min, then 80g of H beta zeolite is added, stirring is carried out for 30min, finally 166g of the modified sol (PA-2) is added, the obtained slurry is homogeneously dispersed (stirred) for 60min, the solid content of the obtained slurry is 25%, then the obtained slurry is spray-dried and molded, and roasting is carried out at 450 ℃ for 1.5H, thus obtaining the catalytic cracking auxiliary CB-2 provided by the invention.
Example 3
(1) Preparation of modified sol: mixing and pulping 36g of pseudo-boehmite, 1.12g of isopropanol and 194g of deionized water for 50min, and uniformly dispersing to obtain a first mixture; then pouring 66g of 85 wt% phosphoric acid solution, continuously stirring at 18 ℃ for 60min, adding the rest 60g of 85 wt% phosphoric acid solution to obtain a second mixture, heating the second mixture to 50 ℃ and stirring for 90min; a modified sol PA-3 having a solids content of 28% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 22.2%, P 2 O 5 The mass content is 77.6%, the P/Al molar ratio is 2.5, the pH value is 2.6, and the average colloidal particle diameter is 25nm.
(2) Preparing modified glue residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 30 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 150 ℃ to obtain solid gumming slag (the solid content is 88 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:20, adding ammonium sulfate which is 20 weight percent of the mass of the gumming residue, then adjusting the pH value of the slurry to 3.5 by using dilute hydrochloric acid with the concentration of 5 weight percent, stirring for 120min at 60 ℃, filtering to obtain solid, and then drying at 150 ℃; and mixing the solid obtained by drying with deionized water according to a mass ratio of 1:20, adding ammonium sulfate which is 20 weight percent of the mass of the gumming residue, then adjusting the pH value of the slurry to 3.5 by dilute hydrochloric acid with the concentration of 5 weight percent, stirring for 120min at 60 ℃, filtering to obtain solid, and then drying again at 150 ℃ to obtain the finished productAccording to analysis, the modified adhesive residue JZ-3 of the formula (I) has Na 2 O content was 0.74 wt%, A1 2 O 3 The content of (C) was 26.5 wt%, siO 2 The content of (C) was 54.9 wt%, RE 2 O 3 The content of (C) was 9.2% by weight, and the specific surface area was 240m 2 Per g, pore volume was 0.8mL/g and average pore diameter was 36nm.
(3) Preparation of catalytic cracking auxiliary agent: 66g of kaolin, 40g of the modified cement residue (JZ-3) and 390g of decationized water are added into a pulping tank for pulping for 60min, 67g of H beta zeolite is added, stirring is carried out for 30min, 214g of the modified sol (PA-3) is finally added, the obtained slurry is homogeneously dispersed (stirred) for 60min, the solid content of the obtained slurry is 25 wt%, and then the obtained slurry is spray-dried and molded, and is roasted for 1H at 550 ℃ to obtain the catalytic cracking auxiliary CB-3 provided by the invention.
Example 4
(1) Preparation of modified sol: mixing 39g of pseudo-boehmite, 1.97g of acetic acid and 194g of deionized water, pulping for 60min, and uniformly dispersing to obtain a first mixture; then pouring 70g of 85 wt% phosphoric acid solution, continuously stirring at 18 ℃ for 60min, adding the rest 50g of 85 wt% phosphoric acid solution to obtain a second mixture, heating the second mixture to 55 ℃ and stirring for 90min; a modified sol PA-4 having a solids content of 35% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 24.5%, P 2 O 5 The mass content is 75.5%, the P/Al molar ratio is 2.2, the pH value is 2.4, and the average colloidal particle diameter is 20nm.
(2) Preparing modified glue residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 20 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 160 ℃, so as to obtain solid gumming slag (the solid content is 90.5 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:15, adding phosphoric acid with the concentration of 20 weight percent to adjust the pH value of the slurry to 3.1, stirring for 120min at 25 ℃, filtering to obtain solid, and then drying at 120 ℃; and mixing the solid obtained by drying with deionized water according to a mass ratio of 1:15, adding phosphoric acid with the concentration of 20 weight percent to adjust the pH value of the slurry to 3.1, stirring for 120min at 25 ℃, filtering to obtain solid, then drying again at 120 ℃,the obtained modified gum residue is JZ-4, and analyzed, na thereof 2 The content of O was 1.23 wt%, A1 2 O 3 The content of (C) was 23.1 wt%, siO 2 The content of (C) was 52.1 wt%, RE 2 O 3 The content of (C) was 9.5% by weight, and the specific surface area was 260m 2 Per g, pore volume was 0.66mL/g and average pore diameter was 28nm.
(3) Preparation of catalytic cracking auxiliary agent: 60g of kaolin, 4g of the modified cement residue (JZ-4) and 428g of decationized water are added into a pulping tank for pulping for 60min, then 107g of H beta zeolite is added, stirring is carried out for 60min, finally 200g of the modified sol (PA-4) is added, the obtained slurry is homogeneously dispersed (stirred) for 40 min, the solid content of the obtained slurry is 25 wt%, and then the obtained slurry is spray-dried and molded, and is roasted for 1H at 500 ℃ to obtain the catalytic cracking auxiliary CB-4 provided by the invention.
Example 5
(1) Preparation of modified sol: mixing and pulping 37g of pseudo-boehmite, 0.69g of oxalic acid and 194g of deionized water for 30min, and uniformly dispersing to obtain a first mixture; then pouring 80g of 85 wt% phosphoric acid solution, continuously stirring for 30min at 18 ℃, adding the rest 45g of 85 wt% phosphoric acid solution to obtain a second mixture, heating the second mixture to 60 ℃, and stirring for 120min; a modified sol PA-5 having a solids content of 35% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 23.1%, P 2 O 5 The mass content is 76.9%, the P/Al molar ratio is 2.4, the pH value is 2.0, and the average colloidal particle diameter is 20nm.
(2) Preparing modified glue residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 25 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 180 ℃ to obtain solid gumming slag (the solid content is 89.2 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:8, adding ammonium sulfate, wherein the ammonium sulfate is 30 weight percent of the mass of the gum residue, adjusting the pH value of the slurry to 3.0 by using dilute hydrochloric acid with a concentration of 5 weight percent, stirring for 120min at 60 ℃, filtering, and drying at 150 ℃; mixing the dried solid with deionized water according to a mass ratio of 1:8, adding ammonium sulfate, wherein the ammonium sulfate is 30 weight percent of the mass of the gumming residue, and then using the concentrationAdjusting pH of the slurry to 3.0 with 5 wt% diluted hydrochloric acid, stirring at 60deg.C for 120min, filtering, and drying at 150deg.C to obtain gum residue JZ-5, na thereof 2 O content was 0.75 wt%, A1 2 O 3 The content of (C) was 26.4 wt%, siO 2 The content of (C) was 55.0 wt%, RE 2 O 3 The content of (C) was 9.1% by weight and the specific surface area was 262m 2 Per g, pore volume 0.85mL/g, average pore diameter 40nm.
(3) Preparation of catalytic cracking auxiliary agent: 126g of kaolin, 10g of the modified cement (JZ-5) and 471g of decationized water are added into a pulping tank for pulping for 60min, 67g of H beta zeolite is added, stirring is carried out for 60min, 125g of the modified sol (PA-5) is finally added, the obtained slurry is homogeneously dispersed (stirred) for 30min, the solid content of the obtained slurry is 25 wt%, and then the obtained slurry is spray-dried and molded, and is roasted at 500 ℃ for 2H, thus obtaining the catalytic cracking auxiliary CB-5 provided by the invention.
Example 6
Catalytic cracking auxiliary CB-6 was prepared by the same method as in example 1, except that the modified sol in step (1) was prepared by the following method:
mixing 52.2g of pseudo-boehmite, 0.65g of ethanol and 149g of deionized water, pulping for 30min, and uniformly dispersing to obtain a first mixture; pouring 110g of 85 wt% phosphoric acid solution into the mixture to obtain a second mixture, heating the second mixture to 45 ℃ and stirring for 180min; a modified sol PA-6 having a solids content of 32% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 32.5%, P 2 O 5 The mass content is 66.8%, the P/Al molar ratio is 1.5, the pH value of the sol is 2.8, and the average colloidal particle diameter is 45nm.
Example 7
Catalytic cracking auxiliary CB-7 was prepared by the same method as in example 1, except that the preparation method of the modified cement in step (2) was different, and the modified cement was prepared by the following method:
stirring the glue residue uniformly, wherein the solid content of the slurry is 20 wt%, spray drying and forming, and the temperature of spray drying tail gas is 200 ℃ to obtain solidGum residue (90.8 wt.% solids); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:15, adding 85 wt% phosphoric acid to adjust the pH value of the slurry to 4.5, stirring at 25 ℃ for 120min, filtering to obtain solid, and drying at 200 ℃; and mixing the solid obtained by drying with deionized water according to a mass ratio of 1:15, adding 85 wt% phosphoric acid to adjust the pH of the slurry to 4.5, stirring at 25deg.C for 120min, filtering to obtain solid, drying again at 200deg.C to obtain modified gum residue, designated JZ-6, and analyzing to obtain Na 2 The content of O was 1.89% by weight, A1 2 O 3 The content of (C) was 22.8 wt%, siO 2 The content of (C) was 48.5 wt%, RE 2 O 3 The content of (C) was 9.0% by weight and the specific surface area was 190m 2 Per g, pore volume was 0.62mL/g and average pore diameter was 19nm.
Example 8
Catalytic cracking promoter CB-8 was prepared in the same manner as in example 1 except that the catalytic cracking promoter of step (3) was prepared by the following method:
26g of kaolin, 50g of the modified cement (JZ-1) and 451g of deionized water are added into a pulping tank for pulping for 60min, 72g of H beta zeolite is added, stirring is carried out for 30min, 238g of the modified sol (PA-1) is finally added, the obtained slurry is subjected to homogeneous dispersion (stirring) for 30min, the solid content of the obtained slurry is 25 wt%, the obtained slurry is subjected to spray drying and forming, and roasting is carried out at 500 ℃ for 2H, so that the catalytic cracking auxiliary CB-8 provided by the invention is obtained.
Comparative example 1
This comparative example illustrates a cracking aid prepared using a conventional phosphorus modified alumina sol and unmodified gum residue.
The phosphorus-modified alumina sol DA3 was prepared according to the method of example 1 in CN1417296A, as follows:
5.8 kg of pseudo-boehmite (containing Al) 2 O 3 1.8 kg) and 4.0 kg of deionized water for 30 minutes, adding 9.6 kg of concentrated phosphoric acid into the slurry under stirring, heating to 70 ℃, and then reacting for 45 minutes at 20 ℃ to obtain colorless and transparent phosphorus-containing aluminum sol. The phosphorus was analyzedAluminum sol containing P 2 O 5 The mass content is 83.3%, al 2 O 3 The mass content is 16.7%, the P/Al molar ratio is 2.7, and the pH value is 1.7.
According to the method of example 1 of the present invention, 79g of kaolin, 20g of unmodified cement and 451g of decationized water were added into a pulping tank to be pulped for 60 minutes, then 93g of H beta zeolite was added, stirring was performed for 30 minutes, finally 156g of the above modified sol (DA 3) was added, and the obtained slurry was homogeneously dispersed (stirred) for 30 minutes, the solid content of the obtained slurry was 25%, and then the obtained slurry was spray-dried and molded, and calcined at 500℃for 2 hours, to obtain a comparative catalytic cracking aid CB-D1, the composition and characteristic parameters of which are shown in Table 2, and the following comparative examples were the same.
Comparative example 2
This comparative example illustrates the use of a conventional phosphorus modified alumina sol and a cracking aid prepared without gum residue.
A phosphorus-modified alumina sol DA3 was prepared in the same manner as in comparative example 1, and analyzed to contain P 2 O 5 The mass content is 83.3%, al 2 O 3 The mass content is 16.7%, the P/Al molar ratio is 2.7, and the pH value is 1.7.
According to the method of example 1 of the present invention, 105g of kaolin and 451g of decationized water were added to a pulping tank to pulp for 60 minutes, then 93g of H beta zeolite was added, stirred for 30 minutes, finally 156g of the above-mentioned modified sol (DA 3) was added, and homogeneously dispersed (stirred) for 30 minutes, the solid content of the obtained slurry was 25%, and then the obtained slurry was spray-dried to form and calcined at 500℃for 2 hours, to obtain comparative catalytic cracking aid CB-D2.
TABLE 1 composition and physicochemical Properties of catalytic cracking aid
Figure BDA0002693338210000171
Figure BDA0002693338210000181
TABLE 2
Figure BDA0002693338210000182
Test case
Catalytic cracking assistants CB1 to CB8 prepared in examples 1 to 8 and CB-D1 to CB-D2 prepared in comparative examples 1 to 2 of the invention are mixed with industrial catalyst (provided by Qilu division Co., ltd., main properties are shown in Table 3) with brand SGC-1 according to a certain proportion to form a catalyst mixture, and the catalyst mixture is subjected to 100% water vapor aging at 800 ℃ for 17 hours on a fixed bed aging device. The raw oil used was then evaluated on an ACE unit and the properties are shown in table 4. The reaction temperature, the catalyst-to-oil ratio, the weight hourly space velocity and the evaluation results are shown in Table 5.
Wherein conversion = gasoline yield + liquefied gas yield + dry gas yield + coke yield; butene concentration in liquefied gas = butene yield/liquefied gas yield.
TABLE 3 Properties of commercial catalysts
Name of the name SGC-1
Chemical composition/%
RE 2 O 3 3.4
Al 2 O 3 52.3
Na 2 O 0.16
Physical Properties
Specific surface area/(m) 2 ×g -1 ) 269
Pore volume/(mL. Times.g) -1 ) 0.38
Bulk density/(g.times.cm) -3 ) 0.75
Sieving mass composition/%
0～20mm 1.5
0～40mm 12.8
0～149mm 90.1
APSmm 76.8
Wear index/(%) 1.2
MA(800℃/4h) 78
TABLE 4 Properties of raw oil
Figure BDA0002693338210000191
Table 5 evaluation results
Figure BDA0002693338210000201
Table 6 evaluation results
Figure BDA0002693338210000202
As can be seen from tables 5 and 6, the catalytic cracking auxiliary agent prepared by the method has excellent butene yield, can obviously improve the concentration of butene in liquefied gas, and has high cracking activity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (8)

1. The catalytic cracking auxiliary agent for increasing the concentration of butene in the liquefied gas comprises, by taking the total weight of the catalytic cracking auxiliary agent as a reference, 10-50 wt% of beta zeolite, 5-40 wt% of modified sol, 2-30 wt% of modified gumming residue and 10-70 wt% of clay;
based on the total weight of the modified cement, the modified cement contains 0-2.0 wt% of Na 2 O, 10-40 wt% of Al 2 O 3 20 to 70 wt% of SiO 2 And 1 to 15 wt% RE 2 O 3 The specific surface area of the modified glue residue is 180-350 m 2 Per gram, the pore volume is 0.6-1.0 mL/g, and the average pore diameter is 10-50 nm;
the modified sol contains 20 to 50 wt% of Al based on the total weight of the modified sol 2 O 3 And 50 to 80 wt% of P 2 O 5 The molar ratio of P to Al is 1.5-2.5, the pH value of the modified sol is 1.5-3.5, and the average colloidal particle diameter is 10-50 nm;
the method for preparing the catalytic cracking auxiliary comprises the following steps: mixing beta zeolite, modified sol, modified glue residue, a first solvent and clay, and then performing first drying and roasting; wherein, the modified rubber residue is prepared by the following steps: mixing the solid glue residue, the second solvent and the acid solution, reacting the obtained slurry at 20-90 ℃ for 30-120 min, and taking out the solid, wherein the pH value of the slurry is 1-5;
the modified sol is prepared by adopting a method comprising the following steps: mixing an aluminum source, water and an organic solvent to obtain a first mixture, and mixing and stirring the first mixture and a first part of phosphoric acid at 40-65 ℃ for 10-60 min to obtain a third mixture; mixing the third mixture with a second part of the phosphoric acid to obtain a second mixture, and reacting the second mixture at 40-65 ℃ for 30-180 min;
the organic solvent is selected from one or more of methanol, ethanol, isopropanol, n-butanol, isobutanol, heptane, n-hexane, cyclohexane, n-octane, acetone, butanone, formic acid, oxalic acid, acetic acid and propionic acid; the weight of the organic solvent is 2-10% of the weight of the aluminum source, and the weight of the aluminum source is calculated by alumina;
the beta zeolite is selected from H beta zeolite and/or modified beta zeolite, wherein the modified beta zeolite contains one or more of phosphorus, iron and rare earth metals;
the acid solution contains organic acid and/or inorganic acid, wherein the organic acid is selected from one or more of oxalic acid, acetic acid and citric acid, and the inorganic acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, ammonium sulfate and ammonium chloride.
2. The catalytic cracking aid according to claim 1, wherein the catalytic cracking aid comprises 10-40 wt% of beta zeolite, 5-35 wt% of modified sol, 2-20 wt% of modified cement and 20-60 wt% of clay.
3. The catalytic cracking aid of claim 1, wherein the process for preparing the catalytic cracking catalyst comprises: mixing and pulping the clay, the modified gumming residue and the solvent to obtain first slurry; and mixing the first slurry, the beta zeolite and the modified sol, and then performing first drying and roasting on the obtained second slurry.
4. The catalytic cracking aid of claim 1, wherein the process for preparing the solid gum residue comprises: performing secondary drying on the glue residue to obtain the solid glue residue;
the solid gum residue has a solid content of 70-95 wt%; based on the dry weight of the solid gum residue, the solid gum residue contains 2-15 wt% of Na 2 O, 10-50 wt% of Al 2 O 3 30-70 wt% of SiO 2 And 1 to 15 wt% RE 2 O 3 。
5. The catalytic cracking aid of claim 1, wherein the first portion of phosphoric acid is 30-70% by weight based on the total weight of the first and second portions of phosphoric acid.
6. The catalytic cracking aid according to claim 1, wherein the clay is one or more selected from kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite and sepiolite;
the first solvent and the second solvent are each independently selected from one or more of deionized water, decationized water and distilled water.
7. Use of the catalytic cracking aid according to any one of claims 1-6 in catalytic cracking of crude oil.
8. The use of claim 7, wherein the conditions for catalytic cracking of crude oil comprise: the temperature is 490-530 ℃, the time is 1-3s, and the catalyst-oil ratio is 3-8;
the content of the catalytic cracking auxiliary agent is 1-50 wt% based on the total weight of the catalytic cracking auxiliary agent and the catalytic cracking catalyst.
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