CN113398979B - Catalyst for preparing fuel oil by catalytic cracking of waste polypropylene plastic and preparation method thereof - Google Patents

Catalyst for preparing fuel oil by catalytic cracking of waste polypropylene plastic and preparation method thereof Download PDF

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CN113398979B
CN113398979B CN202110625527.3A CN202110625527A CN113398979B CN 113398979 B CN113398979 B CN 113398979B CN 202110625527 A CN202110625527 A CN 202110625527A CN 113398979 B CN113398979 B CN 113398979B
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catalyst
molecular sieve
slurry
sio
catalytic cracking
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CN113398979A (en
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王婷
杨朝合
张金庆
谭映临
李正
张新功
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Qingdao Huicheng Environmental Protection Technology Group Co ltd
China University of Petroleum East China
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Qingdao Huicheng Environmental Protection Technology Group Co ltd
China University of Petroleum East China
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
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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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J35/643—Pore diameter less than 2 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
    • 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
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

A catalyst for preparing fuel oil by catalytic cracking of waste polypropylene plastics comprises a silicon dioxide substrate and a molecular sieve, wherein the mass of the silicon dioxide substrate is 20-50 wt% of the mass of the catalyst, and the pore diameter on the silicon dioxide substrate is 20-60 nm; the molecular sieve comprises one or more of Y-type, beta molecular sieve, USY molecular sieve, SBA-15 and MCM-41. By the method, the total oil yield of gasoline and diesel oil can reach more than 90 percent. The NaY mother liquor is recycled in the preparation process of the catalyst, so that on one hand, a path can be provided for treating the NaY mother liquor, and on the other hand, the cost of the catalyst can be reduced.

Description

Catalyst for preparing fuel oil by catalytic cracking of waste polypropylene plastic and preparation method thereof
Technical Field
The invention relates to a catalyst in the field of chemical engineering, in particular to a catalyst used in the field of waste plastic recovery and a preparation method thereof.
Background
The waste plastics recycling mainly comprises four methods of landfill, incineration, physical screening, separation and recycling and oiling technology, the first three methods not only can cause secondary pollution to the ecological environment, but also can harm human health, the oiling technology can crack fuel oil, namely gasoline and diesel oil, the cracked product has high use value, and thus the urgent need of exhaustion of petroleum resources is relieved, natural resources are supplemented, and energy is regenerated. Meanwhile, the requirements of circular economy and environment-friendly economy are met, and huge economic and environmental benefits are brought. Because polypropylene is widely used for preparing drinking cups, straws, packing bags, woven bags and the like, the consumption is large, the oiling of waste polypropylene plastic is very important and meaningful work, and the key of the oiling technology is that the quality of a catalyst directly influences the yield of catalytic cracking. In the prior art, the catalyst specially used for preparing the oil by catalytic cracking of the waste polypropylene plastic is less.
Chinese patent application publication No. CN101168678 discloses a catalyst for preparing fuel oil by cracking polyethylene and polypropylene waste plastics, which is prepared by phosphorus modification of KDC-1 type molecular sieve and kaolin, and the yield of gasoline and diesel oil is about 80%.
Chinese patent application publication No. CN101284235 discloses a catalyst for preparing fuel oil by catalytic cracking of mixed waste plastics and a preparation method thereof, wherein the first stage catalyst consists of 2.0wt% -30.0 wt% of metal oxide and 70.0wt% -98.0 wt% of carclazyte or montmorillonite, the second stage catalyst consists of iron oxide, molybdenum oxide, zinc oxide, cerium oxide, lanthanum oxide, nickel oxide or copper oxide and a ZSM-5, MCM-22, USY, REY, beta or MOR molecular sieve, the cracking gas of the first stage is subjected to secondary catalytic cracking, isomerization and aromatization modification reactions, the fraction ratio of the cracking gasoline and diesel oil is improved, and the qualified fuel oil yield reaches more than 70%. The industry is constantly seeking techniques to increase the oil yield of waste plastic recovery.
Disclosure of Invention
An object of the present invention is to provide a catalyst for catalytic cracking of polypropylene, which can improve the oil yield of waste polypropylene from cracking into fuel oil.
The second purpose of the invention is to provide a preparation method of the catalyst for catalytic cracking of the waste polypropylene.
The third purpose of the invention is to provide a method for catalytic cracking of waste polypropylene, which can improve the oil yield of fuel oil at a relatively low cracking temperature.
In order to realize the aim of the invention, the catalyst for polypropylene catalytic cracking comprises a silicon dioxide matrix and a molecular sieve, wherein the mass of the silicon dioxide matrix is 20-50 wt% of the mass of the catalyst, and the pore diameter on the silicon dioxide matrix is distributed between 20-60 nm; the molecular sieve comprises one or more of Y-type, beta molecular sieve, USY molecular sieve, SBA-15 and MCM-41.
Through the organic combination of the silicon dioxide matrix and the molecular sieve, the waste polypropylene macromolecules can enter a matrix pore channel to carry out a cracking reaction, the diffusion mass transfer of macromolecule raw materials and intermediate products is promoted, the deep reaction on the outer surface and an orifice is avoided, a large amount of coke is generated and the orifice is blocked, and more intermediate products are subjected to the cracking reaction on the molecular sieve to prepare the fuel oil.
A preparation method of a catalyst for polypropylene catalytic cracking comprises the following steps:
adding NaY mother liquor into the slurry of the silica sol and mixing to obtain slurry A, wherein Na is contained in the slurry A 2 O/SiO 2 The mass ratio of (A) is 1:1-2.5;
adding a molecular sieve into the slurry A, and mixing to obtain slurry B;
and granulating the slurry B, and roasting to obtain the catalyst.
The prepared catalyst is applied to the preparation of fuel oil by polypropylene catalytic cracking, wherein the reaction temperature is 300-350 ℃.
By the catalytic cracking method, the total oil yield of gasoline and diesel oil can reach over 90 percent.
Drawings
FIG. 1 is a distribution diagram of the pore diameters of micropores of the catalyst obtained in example 1
FIG. 2 is a mesoporous distribution diagram of the catalyst obtained in example 1
FIG. 3 shows NH of the substrate obtained in example 1 3 -TPD spectrum
Detailed Description
The catalyst for catalytic cracking of waste polypropylene and the preparation method thereof according to the present invention will be described in further detail below. And do not limit the scope of the present application, which is defined by the claims. Certain disclosed specific details provide a thorough understanding of various disclosed embodiments. One skilled in the relevant art will recognize, however, that embodiments may be practiced without one or more of the specific details, with other materials, etc.
Unless the context requires otherwise, in the description and claims, the terms "comprise," comprises, "and" comprising "are to be construed in an open-ended, inclusive sense, i.e., as" including, but not limited to.
Reference in the specification to "an embodiment," "another embodiment," or "certain embodiments," etc., means that a particular described feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, "an embodiment," "another embodiment," or "certain embodiments" do not necessarily all refer to the same embodiments. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. All percentages, ratios, proportions, or parts are by weight unless otherwise specified.
In the present invention, the concentration unit "M" of the solution means mol/L.
A particular type of molecular sieve herein has properties common to that type of molecular sieve. Such as:
y-type molecular sieve (prepared by dividing according to Si/Al ratio) and having general formula of MO- 2 O 3 ﹒SiO 2 ﹒yH 2 O, M represents K, na, ca, etc., siO 2 /Al 2 O 3 The molar ratio is more than 3.0, and the molecular sieve is a Y-type molecular sieve.
The beta molecular sieve is a high-silicon zeolite with three-dimensional twelve-element ring pore structure, and has the structural characteristics of double six-element ring unit crystal cavity structure of two four-element rings and four five-element rings.
SBA-15 is a mesoporous molecular sieve with a two-dimensional hexagonal through-hole structure.
MCM-41 is a long-range ordered mesoporous material with uniform pore size.
In the cracking process of the waste polypropylene, the waste polypropylene is firstly contacted with a surface active center of a catalyst to perform surface catalytic reaction to generate smaller molecular fragments, and the small molecular fragments enter a catalyst pore channel to perform secondary catalytic cracking to generate compounds with smaller molecular weight, so that whether the small molecular fragments can smoothly enter the catalyst pore channel to contact the catalytic center depends on the size of the catalyst pore diameter. By adjusting the pore structure and acid property of the catalyst substrate and the synergistic effect of the catalyst substrate and the molecular sieve, the cracking process of the waste polypropylene is optimized, and the yield of gasoline and diesel oil is improved.
A catalyst for preparing fuel oil by polypropylene catalytic cracking comprises a silicon dioxide substrate and a molecular sieve, wherein the mass of the silicon dioxide substrate is 20-50 wt% of the mass of the catalyst, and the pore diameter on the silicon dioxide substrate is 20-60 nm; the molecular sieve comprises one or more of Y-type, beta molecular sieve, USY molecular sieve, SBA-15 and MCM-41.
The mass of the molecular sieve is 20wt% -50 wt% of the mass of the catalyst.
Preferably, the amount of acid in the silica matrix is 0.3 to 0.8mmol/g.
The acid amount of the silica matrix refers to the amount of the substance of hydrogen protons per unit weight of the matrix. By using NH 3 The TPD method analyzes the acid properties of the matrix.
The catalyst for preparing fuel oil by catalytic cracking of waste polypropylene has a proper matrix pore structure, initial cracking macromolecules of the waste polypropylene after reaction on the surface of the catalyst can enter a matrix pore channel as soon as possible to perform cracking reaction, deep reaction on the outer surface and the pore opening is avoided, coke is generated and the pore opening is blocked, the proper matrix pore structure can promote diffusion mass transfer of the initial cracking macromolecules and intermediate products, and more raw materials are provided for the cracking reaction on a subsequent molecular sieve. Since polypropylene has methyl side chains and is readily available as carbonium ions, it does not require too many acid sites for the cleavage reaction. More preferably, the number of acid centers in the matrix satisfies the acidity requirement for initial cleavage of polypropylene, and the use of this catalyst can greatly reduce the activation energy of the reaction, resulting in a reduction in the cleavage temperature of about 75 ℃.
In certain embodiments, the pore size distribution of the catalyst for catalytic cracking of polypropylene is such that there are two types of pores within 0.5 to 5nm and 20 to 60 nm.
In certain embodiments, the silica matrix has a pore volume of 0.8 to 1.2cm 3 (ii) in terms of/g. Further, the specific surface area of the silica matrix is 300 to 500m 2 /g。
The pore size distribution of the molecular sieve is between 0.5 and 5nm.
In some embodiments, the catalyst for preparing fuel oil by catalytic cracking of polypropylene further comprises a binder, wherein the binder comprises silica, and the mass of the binder is 10wt% to 30wt% of the mass of the catalyst.
In certain preferred embodiments, the Y-type molecular sieve is loaded with a rare earth element. The performance of the catalytic cracking waste polypropylene fuel oil is superior to that of a molecular sieve which does not load rare earth elements.
The catalyst for polypropylene catalytic cracking with the characteristics can be prepared by various methods. In the present application, the following method is used, among others.
On the other hand, the preparation method of the catalyst for polypropylene catalytic cracking comprises the following steps:
adding NaY mother liquor into the slurry of the acidic silica sol and mixing to obtain slurry A, wherein Na in the slurry A 2 O/SiO 2 The ratio of the amount of the substances is 1:1-2.5, H in the acidic silica sol + /SiO 2 The mass ratio of the substances is between 0.1 and 1.0;
adding a molecular sieve into the slurry A, and mixing to obtain slurry B;
and granulating the slurry B, and roasting to obtain the catalyst.
The main components of the NaY mother liquor contain sodium element and silicon element, wherein the sodium element is Na 2 The content is 15 g/L-30 g/L calculated by O; silicon element is SiO 2 The content is 30g/L to 60g/L.
In certain embodiments, a slurry of silica sol is mixed with a NaY mother liquor at a temperature of 30 to 60 ℃. Preferably, the temperature is between 35 and 50 ℃.
The mixing time of the slurry of the silica sol and the NaY mother liquor is controlled to be 20 min-60 min.
In the slurry A, na 2 O/SiO 2 In the proportional relationship of the amounts of substances, na 2 O represents the amount of NaY mother liquor, siO 2 Denotes SiO in silica sol 2 The amount of (c).
By controlling the reaction conditions, the size of the silica gel particles generated by the reaction can be controlled, and the pore structure size of the formed silica matrix can be further controlled.
In certain embodiments, the acidic silica sol is SiO 2 Meter, siO 2 25-50 wt% of acid silica sol.
An appropriate amount of acid can be added into the acidic silica sol to adjust the ratio of hydrogen ions to silicon dioxide in the acidic silica sol, namely H + /SiO 2 The mass ratio of the substances is between 0.1 and 1.0. The added acid includes, but is not limited to, one of hydrochloric acid, sulfuric acid, boric acid, or phosphoric acid.
In certain embodiments, in the acidic silica sol, H + /SiO 2 The mass ratio is between 0.2 and 0.5.
In some embodiments, the molecular sieve is added in an amount such that the molecular sieve is in contact with the SiO in slurry A 2 The mass ratio of (a) is 1:4-1:1.
In the actual treatment process, the preparation conditions of the matrix and the proportion and the type of the molecular sieve are properly adjusted according to the specific requirements of the yield of fuel oil (gasoline and diesel oil) and the diesel-gasoline ratio.
In certain embodiments, na 2 O/SiO 2 The ratio of the amount of the substances is 1:1-2.5. Under the condition, the mesoporous structure of the silicon dioxide matrix in the obtained catalyst is more uniform and more.
In the application, the silicon dioxide matrix and the molecular sieve are bonded together through the silicon-based binder, and compared with an aluminum-based binder or a silicon-aluminum binder, the catalyst prepared by using the silicon-based binder is used in the reaction of preparing fuel by catalytic cracking of waste polypropylene, so that the coke yield is low.
In the application, the roasting temperature is controlled to be 450-600 ℃. Preferably, the roasting temperature is controlled to be 500-600 ℃.
In certain embodiments, the calcined catalyst is washed with water and dried. The drying temperature is controlled to be about 100 ℃, and the moisture can be evaporated to dryness.
The catalyst provided by the application can be used for catalytically cracking waste polypropylene plastics or waste modified polypropylene plastics. Common polypropylene waste plastics types, such as drinking cups, straws, woven bags, and the like.
The polypropylene catalytic cracking catalyst selects the silicon dioxide substrate with large particle size, can effectively promote the diffusion mass transfer of polypropylene macromolecular raw materials and intermediate products, has high utilization rate of acid sites, improves the yield of gasoline and diesel oil in a cracked oil product, and simultaneously has better coke selectivity and hydrothermal stability and can be repeatedly used. The catalyst can reduce the polypropylene cracking temperature by about 75 ℃, and the gasoline and diesel oil yield is improved to more than 90%.
The catalyst preparation method can solve the recycling problem of the NaY mother liquor, the production amount of the NaY mother liquor is far larger than the recycling amount at present, and the NaY mother liquor is recycled into the catalyst for preparing fuel oil by catalytic cracking of waste polypropylene plastics, so that on one hand, a path can be provided for treating the NaY mother liquor, and on the other hand, the cost of the catalyst can be reduced.
The catalyst of the present invention and its catalytic effect are further illustrated below with reference to specific examples.
Example 1:
(1) At room temperature, to silica Sol (SiO) 2 Acid silica sol with a content of 30%) is added with hydrochloric acid to obtain a slurry so that H is + /SiO 2 The mass ratio of (A) is 0.2, and the mixture is fully stirred for 10min;
(2) Adding NaY mother liquor (SiO) into the slurry in the step (1) 2 The concentration is 50g/L, na 2 O concentration of 25 g/L) so that Na in NaY mother liquor 2 O and SiO in the slurry in the step (1) 2 The quantity ratio of substances is 1, the temperature is controlled to be 30 ℃, and the reaction is carried outObtaining slurry A after 20 min;
(3) Adding REUSY molecular sieve (representing USY molecular sieve containing rare earth elements, wherein La and La elements are added, the content is 2wt% of the molecular sieve) into the slurry A in the step (2), and stirring for 1h at room temperature to obtain slurry B, wherein the molecular sieve and all Si elements in the slurry A are SiO 2 The calculated mass ratio is 1.86.
(4) And (4) carrying out spray granulation on the slurry B obtained in the step (3), roasting at 500 ℃, washing, and drying at 100 ℃, and recording as a fuel oil catalyst Cat-1 prepared by catalytic cracking of waste polypropylene. In Cat-1, the matrix silica content was 44wt% and the molecular sieve content was 35wt%
The pore size distribution of micropores of the catalyst Cat-1 is shown in figure 1, the micropores are provided by a molecular sieve, the pore size is about 0.8nm, the pore size distribution of mesopores is shown in figure 2, the mesopores are provided by a substrate, and the pore size is about 30 nm. In FIGS. 1-2, the ordinate "dV/dlogW" is the differential value of pore volume versus pore diameter. The acid amount distribution of the matrix is shown in figure 3, most of the acid amount distribution is weak acid sites, and a small number of strong acid sites exist, so that the requirement of plastic pre-cracking on the acid amount can be met.
Example 2:
(1) At room temperature, to silica Sol (SiO) 2 Acid silica sol with a content of 30%) is added with hydrochloric acid to obtain a slurry so that H is + /SiO 2 The mass ratio of (A) is 0.3, and the mixture is fully stirred for 10min;
(2) Adding NaY mother liquor (SiO) into the slurry in the step (1) 2 The concentration of the sodium hydroxide is 45g/L, na 2 O concentration of 22 g/L) so that Na in NaY mother liquor 2 O and SiO in the slurry in the step (1) 2 The mass ratio of the substances is 1.5, the temperature is controlled to be 35 ℃, and the reaction is carried out for 30min to obtain slurry A;
(3) Adding USY molecular sieve into the slurry A in the step (2), and stirring for 1h at room temperature to obtain slurry B, wherein the molecular sieve and all Si elements in the slurry A are in SiO 2 The calculated mass ratio is 1.86. (ii) a
(4) And (4) carrying out spray granulation on the slurry B obtained in the step (3), roasting at 500 ℃, washing with water, and drying at 100 ℃, and recording as the fuel oil catalyst Cat-2 prepared by catalytic cracking of waste polypropylene. In Cat-2, the content of matrix silica was 49wt%; the content of molecular sieve was 35wt%.
Example 3:
(1) At room temperature, to silica Sol (SiO) 2 Acid silica sol with a content of 30%) is added with hydrochloric acid to obtain a slurry so that H is + /SiO 2 The mass ratio of (A) is 0.5, and the mixture is fully stirred for 10min;
(2) Adding NaY mother liquor (SiO) into the slurry in the step (1) 2 The concentration is 55g/L, na 2 O concentration of 30 g/L) so that Na in NaY mother liquor 2 O and SiO in the slurry in the step (1) 2 The mass ratio of the substances is 1.75, the temperature is controlled to be 40 ℃, and the reaction is carried out for 40min to obtain slurry A;
(3) Adding an MCM-41 molecular sieve into the slurry A in the step (2), and stirring for 1h at room temperature to obtain slurry B, wherein the molecular sieve and all Si elements in the slurry A are SiO 2 1.86 by mass ratio;
(4) And (4) performing spray granulation on the slurry B obtained in the step (3), roasting at 550 ℃, washing with water, and drying at 100 ℃, wherein the slurry B is marked as a fuel oil catalyst Cat-3 prepared by catalytic cracking of waste polypropylene. In Cat-3, the content of matrix silica is 50% by weight; the content of molecular sieve was 35wt%.
Example 4:
(1) At room temperature, to silica Sol (SiO) 2 Acid silica sol with a content of 30%) is added with hydrochloric acid to obtain a slurry so that H is + /SiO 2 The mass ratio of (A) is 0.65, and fully stirring is carried out for 10min;
(2) Adding NaY mother liquor (SiO) into the slurry in the step (1) 2 The concentration is 55g/L, na 2 O concentration of 30 g/L) so that Na in NaY mother liquor 2 O and SiO in the slurry in the step (1) 2 The mass ratio of the substances is 2.1, the temperature is controlled to be 45 ℃, and the reaction is carried out for 45min to obtain slurry A;
(3) Adding SBA-15 molecular sieve into the slurry A in the step (2), and stirring for 1h at room temperature to obtain slurry B, wherein the molecular sieve and all Si elements in the slurry A are in SiO 2 1.86 by mass ratio;
(4) And (4) performing spray granulation on the slurry B obtained in the step (3), roasting at 550 ℃, washing with water, drying at 100 ℃, and recording as the fuel oil catalyst Cat-4 prepared by catalytic cracking of waste polypropylene. In Cat-4, the content of matrix silica was 52wt%; the content of molecular sieve was 35wt%.
The pore diameter structures of the catalysts Cat-2, cat-3 and Cat-4 obtained in examples 2-4 were also distributed to have two types of pores within 0.5-5 nm and 20-60 nm.
Comparative example 1:
(1) Uniformly mixing 100g of kaolin and 40g of KDC-1 type molecular sieve, and drying in a drying box at 120 ℃ for 2 hours;
(2) Adding 400g of 10% phosphoric acid solution into the mixture, stirring, and standing for 2 hours;
(3) Placing the mixture after standing in a drying oven to dry for 4h at 120 ℃;
(4) Roasting at 500 deg.c for 4 hr;
(5) The catalyst was removed and pressed to crush and sieved to obtain 20-40 mesh particles, which were designated as catalyst Cat-5.
Evaluation of catalyst: the evaluation of the catalyst is carried out on a fixed fluidized bed, 100-mesh polypropylene particles are selected as raw materials, the feeding amount is 500g, the reaction temperature is 300 ℃, and the space velocity is 10h -1 The evaluation results are shown in the following table, wherein the dose ratio is 0.1.
Catalyst and process for preparing same Cat-1 Cat-2 Cat-3 Cat-4 Cat-5
Gasoline yield/wt% 48 46 45 45 43
Diesel oil yield/wt% 42 44 46 48 39
Fuel oil yield per wt% 90 90 91 93 82

Claims (2)

1. A preparation method of a catalyst for preparing fuel oil by catalytic cracking of waste polypropylene plastics comprises the following steps:
adding NaY mother liquor into the slurry of the acidic silica sol and mixing to obtain slurry A, wherein Na in the slurry A 2 O/SiO 2 The mass ratio of (A) is 1:1-2.5; mixing the slurry of the silica sol and NaY mother liquor at the temperature of 35-50 ℃, and controlling the mixing time to be 20-60 min; h in acidic silica sol + /SiO 2 The mass ratio of (A) is between 0.1 and 1:1;
adding a molecular sieve into the slurry A, and mixing to obtain slurry B; molecular sieve and SiO in slurry A 2 The mass ratio of 1:4-1:1; the molecular sieve comprises one or more of Y-type molecular sieve, beta molecular sieve, USY molecular sieve, SBA-15 and MCM-41;
and granulating the slurry B, and roasting to obtain the catalyst.
2. The method for preparing the catalyst for preparing fuel oil by catalytic cracking of waste polypropylene plastic according to claim 1, wherein the preparation of the acidic silica sol comprises: adding an acidic solution to the silica sol to adjust H in the silica sol + /SiO 2 The mass ratio of the substances is between 0.1 and 1.0;
the acidic solution includes one of hydrochloric acid, sulfuric acid, boric acid, or phosphoric acid.
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