CN113398982B - Catalyst for preparing low-carbon olefin by catalytic cracking of waste plastic and preparation method thereof - Google Patents

Catalyst for preparing low-carbon olefin by catalytic cracking of waste plastic and preparation method thereof Download PDF

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CN113398982B
CN113398982B CN202110626073.1A CN202110626073A CN113398982B CN 113398982 B CN113398982 B CN 113398982B CN 202110626073 A CN202110626073 A CN 202110626073A CN 113398982 B CN113398982 B CN 113398982B
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mass
molecular sieve
catalyst
solution
silicon
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CN113398982A (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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/647—
    • B01J35/69—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • 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

Abstract

A catalyst for preparing low-carbon olefin by catalytic cracking waste plastics is composed of Si-Al substrate and molecular sieve, where the Si-Al substrate includes Si-contained substance, al-contained substance and SiO 2 The mass of the silicon-containing substance accounts for 10 to 40 weight percent of the mass of the catalyst, and Al 2 O 3 The mass of the aluminum-containing substance accounts for 30-60 wt% of the mass of the catalyst, and the pore size of the silicon-aluminum substrate is distributed at 5-200 nm; the molecular sieve comprises a ZSM-5 molecular sieve or/and a ZSM-11 molecular sieve; the molecular sieve accounts for 10-40 wt% of the catalyst. The prepared catalyst is applied to preparing low-carbon olefin by catalytic cracking of waste plastics, so that the yield of the low-carbon olefin is improved, and the quality of gasoline is improved.

Description

Catalyst for preparing low-carbon olefin by catalytic cracking of waste 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
Plastics are important components in the field of modern materials, and are widely applied worldwide due to the characteristics of low price, good comprehensive performance and the like. However, plastic products bring convenience to people's lives, and simultaneously generate a large amount of waste, and the ' white pollution ' becomes a prominent problem of environmental protection. The conventional waste plastic treatment methods are a landfill method and a incineration method, and both of these recycling methods have serious problems. The landfill method not only wastes precious land resources, but also destroys the soil structure and pollutes the soil and underground water resources; although the incineration method avoids land resource invasion and can recover partial heat energy, a large amount of waste gas is discharged to cause serious atmospheric pollution. The preparation of the bio-fuel oil or the chemicals with high added value by the catalytic pyrolysis of the waste plastics is an ideal recycling treatment mode developed in recent years. In recent years, there are many reports on methods for preparing fuel oil by cracking waste plastics, and many waste plastic cracking fuel oil preparing devices are also established domestically, but the prior art has the following obvious defects: the cracking and vaporizing process of waste plastics into oil is a gap or semi-batch kettle type operation process, and the catalyst is often directly applied to the catalyst for cracking crude oil. Although there are many similarities between cracking of waste plastics and cracking of crude oil, which are that a macromolecular hydrocarbon structure is pyrolyzed and degraded into a smaller molecular structure under an oxygen-free condition, the chemical properties of crude oil are greatly different from those of waste plastics, the crude oil composition structure is more complex, while the waste plastics have a larger molecular weight but a single component structure, which causes a great difference between the two reaction processes of cracking crude oil and waste plastics, for example, the direct application of a catalyst for cracking crude oil to cracking of waste plastics can cause various problems: a, the existing waste plastic cracking catalyst is carclazyte or silicon-aluminum oxide, has simple components and single function and is only used for reducing the cracking reaction temperature; most of the cracking and modifying catalysts B are petroleum refining catalysts, most of the cracking and modifying catalysts B are REY or USY zeolite, the cracking and modifying catalysts B are simple in function, can only further crack macromolecules in crude oil into small molecules, cannot selectively increase the ratio of gasoline and diesel oil components, and have large gas by-products; in the kettle type cracking process of the C waste plastic, single-function solid acid or cheap argil (active silicon dioxide) is used as a catalyst, the distribution range of waste plastic cracking products is too wide, a large amount of heavy oil and gas are generated, the light oil ratio is low, and particularly, the cracking oiling of mixed waste plastic is difficult to control; d, because the components of the waste plastics are complex, the chlorine content in part of the waste polyethylene plastics is sometimes as high as 10%, the problem of unstable quality of oil products generated by cracking the waste plastics by simply applying a crude oil cracking catalyst is solved, and the waste plastics can only be used as low-grade products such as boiler fuel oil and the like; e domestic and foreign similar cracking and oiling processes for waste plastics have strict requirements on pre-selection and pretreatment of the treated waste plastics, and if the waste plastics need to be classified, cleaned and dried, part of the processes need high-temperature hydrogenation or cracking under pressure.
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%.
The target products of the existing waste plastic cracking are fuel oil and high molecular wax, and the attention degree of the gas-phase products as fuel gas is low. However, most of the gas-phase products are ethylene, propylene, butylene and the like, which are used as important chemical raw materials, and the demand is increasing in recent years, so that the ethylene, propylene and butylene which are used as main target products have stronger market guidance and higher economic benefits.
Disclosure of Invention
An object of the present invention is to provide a catalyst for producing low-carbon olefins by catalytic cracking of waste plastics, which can improve the yield of low-carbon olefins produced by cracking waste plastics.
The second purpose of the invention is to provide a preparation method of the catalyst for preparing low-carbon olefin by catalytic cracking of waste plastic.
The third purpose of the invention is to provide a method for preparing low-carbon olefin by waste plastic catalytic cracking.
In order to realize the purpose of the invention, the catalyst for preparing the low-carbon olefin by the catalytic cracking of the waste plastics comprises a silicon-aluminum substrate and a molecular sieve, wherein the silicon-aluminum substrate comprises a silicon-containing substance and an aluminum-containing substance, and SiO 2 The mass of the silicon-containing substance accounts for 20-50 wt% of the mass of the catalyst, and Al 2 O 3 The mass of the aluminum-containing substance accounts for 20-40 wt% of the mass of the catalyst, and the pore size distribution of the silicon-aluminum substrate is 20-200 nm; the molecular sieve comprises a ZSM-5 molecular sieve or/and a ZSM-11 molecular sieve; the molecular sieve accounts for 10-40 wt% of the catalyst.
Through the organic combination of the silicon-aluminum substrate with the hierarchical pores and the ZSM-5 molecular sieve or/and the ZSM-11 molecular sieve, the waste plastic macromolecules can enter the pore channels of the silicon-aluminum substrate to carry out cracking reaction, and the diffusion mass transfer of the plastic macromolecule raw materials and the intermediate products is promoted. So that the intermediate product diffuses into the pore channels of the molecular sieve for further cracking reaction. Avoiding deep cracking on the outer surface and producing a large amount of coke.
A preparation method of a catalyst for preparing low-carbon olefin by catalytic cracking of waste plastic comprises the following steps:
mixing solution A obtained by mixing pseudo-boehmite and alkali metal hydroxide solution with sodium silicate to obtain solution B, wherein SiO in silicate in mixed solution B 2 With Al in pseudo-boehmite 2 O 3 The mass ratio of the substances is SiO 2 /Al 2 O 3 ＝(0.05～2)：1；
And adding an ammonium dihydrogen phosphate solution into the solution B, adjusting the pH to be less than 10, and standing to generate precipitates in the solution B.
Filtering and washing the precipitate, wherein the filter cake is a silicon-aluminum matrix material;
mixing a silicon-aluminum substrate and a molecular sieve in water to obtain slurry C, wherein the molecular sieve comprises a ZSM-5 molecular sieve or/and a ZSM-11 molecular sieve;
the slurry C was spray dried to obtain the final catalyst.
The prepared catalyst is applied to the preparation of low-carbon olefin by the catalytic cracking of waste plastics, wherein the reaction temperature is 450-550 ℃.
The method catalytically cracks the waste plastics, improves the yield of the low-carbon olefin and improves the quality of the gasoline.
Drawings
FIG. 1 particle size distribution diagram of catalysts obtained in examples 1 and 3
Detailed Description
The catalyst for producing low-carbon olefins by catalytic cracking of waste plastics and the method for producing the same 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:
the ZSM-5 molecular sieve contains ten-membered rings, and a basic structural unit consists of eight five-membered rings. The chemical composition of the ZSM-5 molecular sieve can be expressed as the mole ratio of oxides: 0.9. + -. 0.2M 2/n O:Al 2 O 3 ：5---100SiO 2 :ZH 2 O, wherein M is a cation (alkali metal sodium ion and organic amine ion); n is the valence of the cation; z is from 0 to 40.
The ZSM-11 molecular sieve is a member of high-silicon ZSM series, belongs to Pentasil type zeolite, and is formed by intersecting elliptical ten-membered ring three-dimensional straight channels.
Waste plastics: is a general name of used plastics which are finally eliminated or replaced in civil and industrial applications, and common waste plastics include PE, PP, PVC, PET, EPS, PA and ABS.
The inventor discovers that the molecular sieve and modified molecular sieve catalyst for waste plastic cracking have the characteristics of unique acidity, shape-selective selectivity and the like when analyzing the waste plastic cracking catalyst in the prior art, but if the molecular sieve is used as the catalyst only, hydrocarbon macromolecules generated by plastic pyrolysis are easy to further polymerize on the surface active sites of the molecular sieve, coke is formed to cover the active sites of the molecular sieve, pore channels of the molecular sieve are blocked, the molecular sieve catalyst is quickly inactivated, good product distribution cannot be obtained, the use cost of the catalyst is higher, and the industrial application is difficult. And the substrates used by the existing molecular sieve catalyst are clay substrates, the specific surface and the pore volume are both low, and the requirement of the primary cracking reaction of waste plastics cannot be met. The important purpose of the present application is to develop a catalyst which can crack waste plastics to obtain low-carbon olefins and has high gasoline quality. The specific scheme is as follows.
A catalyst for preparing low-olefine by catalytic cracking waste plastics is composed of Si-Al substrate and molecular sieve, the Si-Al substrate contains Si-contained substance and Al-contained substance, and SiO 2 The mass of the silicon-containing substance accounts for 10 to 40 weight percent of the mass of the catalyst, and Al 2 O 3 The mass of the aluminum-containing substance accounts for 30-60 wt% of the mass of the catalyst, and the pore size of the silicon-aluminum substrate is distributed at 5-200 nm; the molecular sieve comprises a ZSM-5 molecular sieve or/and a ZSM-11 molecular sieve; the molecular sieve accounts for 10-40 wt% of the catalyst.
Preferably, the silica-alumina matrix further comprises a phosphorus oxide, with P 2 O 5 The mass of the phosphorus oxide accounts for 1.5-7.0 wt% of the mass of the catalyst.
In certain embodiments, the silica alumina substrate has a pore size distribution of 5 to 200nm.
Preferably, the ratio of pores with the pore diameter of 5 nm-20 nm in the pores of the silicon-aluminum substrate is 20-40%; the ratio of pores having a pore diameter of more than 2nm and 200nm or less is 20 to 80%.
The ZSM-5 or ZSM-11 may be a microporous molecular sieve as disclosed in the prior art, having a pore size of less than 2nm.
By combining the silicon-aluminum substrate with the hierarchical pore structure and the ZSM-5 or ZSM-11 molecular sieve (both the ZSM-5 molecular sieve and the ZSM-11 are highly selective molecular sieves), the cracking reaction of C6-C9 components in gasoline can be carried out in the pore channel of the ZSM-5 or ZSM-11 molecular sieve to generate C3 and C4, and the isomerization and aromatization reactions can also be carried out to improve the octane number of the gasoline, thereby not only improving the yield of low-carbon olefin, but also improving the quality of the gasoline.
In the silicon-aluminum matrix, the pore volume of the silicon-aluminum matrix is 0.8-1.3 cm 3 (ii) in terms of/g. Preferably, the specific surface area of the silicon-aluminum substrate is 380 to 550m 2 /g。
The catalyst for preparing the low-carbon olefin by the catalytic cracking of the waste plastic 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 preparing the low-carbon olefin by the catalytic cracking of the waste plastic comprises the following steps:
(1) Mixing solution A obtained by mixing pseudo-boehmite and alkali metal hydroxide solution with silicate to obtain solution B, wherein SiO in silicate in mixed solution B 2 With Al in pseudo-boehmite 2 O 3 Mass ratio of substance SiO 2 /Al 2 O 3 ＝(0.05～2)：1；
(2) Adding an ammonium dihydrogen phosphate solution into the solution B, adjusting the pH to be less than 10, and standing to generate a precipitate in the solution B;
filtering the solution B containing the precipitate, wherein a filter cake is a silicon-aluminum substrate material;
(3) Mixing a silicon-aluminum substrate and a molecular sieve in water to obtain slurry C, wherein the molecular sieve comprises a ZSM-5 molecular sieve or/and a ZSM-11 molecular sieve;
the slurry C was spray dried to obtain the final catalyst.
In certain embodiments, the alkali metal hydroxide is sodium hydroxide and the amount of pseudoboehmite and sodium hydroxide used is Al 2 O 3 /Na 2 The mass ratio of O is between 0.1 and 0.9.
Preferably, the reaction temperature of the pseudoboehmite and the sodium hydroxide solution is controlled between 80 and 140 ℃.
Here, the concentration of sodium hydroxide is not particularly required as long as the above-mentioned requirements can be obtained.
In certain embodiments, al is 2 O 3 Adding 10-40 wt% of pseudo-boehmite powder into 30-50wt% of NaOH solution, and controlling the reaction temperature to be 80-140 ℃ to obtain solution.
In some embodiments, the pseudoboehmite and the sodium hydroxide are used in an amount of Al 2 O 3 /Na 2 The mass ratio of O is between 0.13 and 0.7.
In certain embodiments, in step (1), the mass ratio of silica to alkali metal oxide is 3.0.
The silicate may be a water-soluble silicate including sodium silicate and/or potassium silicate.
Preferably, siO in silicate in the mixed solution B 2 With Al in pseudo-boehmite 2 O 3 Mass ratio of substance SiO 2 /Al 2 O 3 ＝(0.25～1)：1
In the step (2), ammonium dihydrogen phosphate is added into the mixed solution, the pH is adjusted to be less than 10, and the temperature is controlled to be 20-30 ℃. Adding a proper amount of ammonium dihydrogen phosphate to obtain the silicon-aluminum substrate with a hierarchical pore structure, wherein the pore diameters of the two pore structures are respectively between 5-20 nm and 20-200 nm (provided by the silicon-aluminum structure precipitated by adding the ammonium dihydrogen phosphate).
Preferably, in the step (2), ammonium dihydrogen phosphate is added to the mixed solution, and the pH is adjusted to 6.0 to 9.0.
Because the steric hindrance of each waste plastic is different and the cracking difficulty is also different, the most probable pore diameter of the silicon-aluminum structure is adjusted according to the specific waste plastic type, so that the diffusion mass transfer of a plastic macromolecular raw material and an intermediate product is promoted, the intermediate product is diffused into a molecular sieve pore channel in time to carry out the next cracking reaction, and the deep cracking on the outer surface is avoided to generate a large amount of coke;
the catalyst prepared by the method can be used for preparing low-carbon olefins by catalytically cracking most of waste plastics, such as: PE, PP, PS, PVC, etc.
For waste plastics which are difficult to crack, the silicon-aluminum ratio and the ammonium dihydrogen phosphate ratio in the silicon-aluminum matrix in the method can be adjusted, the acid centers of the matrix (namely the catalyst contains the silicon-aluminum ratio and the content of phosphorus oxide) are increased, the speed of forming carbonium ions by the waste plastics is accelerated, the catalytic cracking reaction is enhanced, the occurrence of thermal cracking reaction is reduced, and the distribution of products of initial cracking is optimized.
In certain embodiments, in step (3), the silica-alumina substrate is slurried with water to provide a slurry, the molecular sieve is added to the slurry and mixed to provide slurry C.
The amount of water added is generally such that the solids content of slurry C is controlled to about 30% by weight.
The slurry C was spray dried to obtain the final catalyst.
In some embodiments, solution a is mixed with sodium silicate at a temperature of 20 to 50 ℃.
Preferably, the solution A and the sodium silicate are mixed for 5 to 40 hours at the temperature of 20 to 50 ℃.
The adding amount of the molecular sieve is that the ratio of the mass of the molecular sieve dry powder to the dry basis mass of the silicon-aluminum substrate is controlled to be 1:9-4:5.
In the present application, the slurry C is spray-dried at a temperature of 260 to 320 ℃.
The catalyst for preparing low-carbon olefin by catalytic cracking of waste plastic adopts the silicon-aluminum substrate with the multilevel pores, the silicon-aluminum substrate with the multilevel pores can obviously improve the initial cracking reaction product of waste plastic macromolecules, and the catalyst can be reasonably matched with ZSM-5 and/or ZSM-11 molecular sieves to realize the purpose of producing more low-carbon olefin.
In addition, isomerization and aromatization reactions can also occur, the octane number of the gasoline is improved, the yield of the low-carbon olefin can be obviously improved, and the quality of the gasoline can be improved.
The catalyst of the present invention and its catalytic effect are further illustrated below with reference to specific examples.
Example 1:
(1) Adding 10wt% (calculated as alumina) of pseudo-boehmite powder into 30wt% of sodium hydroxide solution, controlling the reaction temperature at 100 ℃, and reacting for 5h, wherein the Al is calculated by the amount of substance 2 O 3 /Na 2 O =0.13, noted as solution a;
(2) The concentration was 250g/l (in SiO) 2 Calculated by the weight of the substance, siO) is added into the solution A, the temperature is controlled to be 40 ℃, and the reaction is carried out for 15 hours, wherein the amount of the substance is taken as the unit 2 /Al 2 O 3 =0.30, note solution B;
(3) Dropwise adding 1mol/L ammonium dihydrogen phosphate solution into the solution B, controlling the pH =9.75, controlling the temperature at 20 ℃, and standing and aging for 0.5h to obtain a precipitate;
(4) Washing the obtained precipitate with chemical water, filtering to obtain silicon-aluminum matrix, adding chemical water, pulping, and recording as slurry C;
(5) Adding ZSM-5 molecular sieve dry powder into the slurry C, and uniformly stirring to obtain slurry D, wherein the ratio of the mass of the ZSM-5 molecular sieve dry powder to the dry mass of the silicon-aluminum matrix obtained in the step (4) is 4:6;
(5) And (3) carrying out spray drying on the slurry D at 260 ℃, and recording the slurry D as a low-carbon olefin catalyst Cat-1 prepared by catalytic cracking of waste plastics.
In the prepared catalyst Cat-1, the ZSM-5 molecular sieve accounts for about 40 percent of the mass of the catalyst, and SiO 2 The mass of the silicon-containing substance accounted for about 8.5% of the mass of the catalyst, al 2 O 3 The mass of the aluminum-containing substance accounted for about 50% of the mass of the catalyst, and the phosphorus pentoxide was about 1.5%. The particle size distribution is shown in figure 1.
Example 2:
(1) 20 percent of pseudo-boehmite powder (calculated by alumina)Adding into 35% sodium hydroxide solution, controlling reaction temperature at 110 deg.C, reacting for 10 hr, wherein Al 2 O 3 /Na 2 O =0.28, noted as solution a;
(2) The concentration was adjusted to 300g/l (in SiO) 2 Meter) is added into the solution A, the temperature is controlled at 45 ℃, the reaction is carried out for 16h, wherein SiO is carried out 2 /Al 2 O 3 =0.45, as solution B;
(3) Dropwise adding 1mol/L ammonium dihydrogen phosphate solution into the solution B, controlling the pH =9.5 and the temperature at 22 ℃, and statically aging for 0.6h;
(4) Washing with chemical water, filtering, adding chemical water, pulping, and recording as pulp C;
(5) Adding ZSM-5 molecular sieve dry powder into the slurry C, uniformly stirring, and recording as slurry D, wherein the ratio of the mass of the ZSM-5 molecular sieve dry powder to the dry-basis mass of the silicon-aluminum matrix obtained in the step (4) is 4:6;
(5) And (3) spray-drying the slurry D at 270 ℃, and recording as a catalyst Cat-2 for preparing the low-carbon olefin by catalytic cracking of the waste plastic.
In the prepared catalyst Cat-2, the ZSM-5 molecular sieve accounts for about 40 percent of the mass of the catalyst, and SiO 2 The mass of the silicon-containing substance accounted for about 11% of the mass of the catalyst, al 2 O 3 The mass of the aluminum-containing material accounted for about 45% of the mass of the catalyst, with the remainder being about 4% phosphorus pentoxide.
Example 3:
(1) Adding 30% (calculated by alumina) of pseudo-boehmite powder into 40% of sodium hydroxide solution, controlling the reaction temperature at 120 ℃, and reacting for 15h, wherein Al is 2 O 3 /Na 2 O =0.35, denoted as solution a;
(2) The concentration was 350g/l (in SiO) 2 Meter) is added into the solution A, the temperature is controlled to be 35 ℃, the reaction is carried out for 17 hours, wherein SiO is carried out 2 /Al 2 O 3 =0.6, note solution B;
(3) Dropwise adding 1mol/L ammonium dihydrogen phosphate solution into the solution B, controlling the pH =9.0 and the temperature at 25 ℃, and standing and aging for 1h;
(4) Washing with chemical water, filtering, adding chemical water, pulping, and recording as pulp C;
(5) Adding ZSM-5 molecular sieve dry powder into the slurry C, uniformly stirring, and recording as slurry D, wherein the ratio of the mass of the ZSM-5 molecular sieve dry powder to the dry-basis mass of the silicon-aluminum matrix obtained in the step (4) is 4:6;
(5) And (3) spray-drying the slurry D at 280 ℃, and recording as a low-carbon olefin catalyst Cat-3 prepared by catalytic cracking of waste plastics.
In the prepared catalyst Cat-3, the ZSM-5 molecular sieve accounts for about 40 percent of the mass of the catalyst, and SiO 2 The mass of the silicon-containing substance accounted for about 14% of the mass of the catalyst, al 2 O 3 The mass of the aluminum-containing material accounted for about 43% of the mass of the catalyst, with the remainder being about 3% of the phosphorus pentoxide.
Example 4:
(1) Adding 35% (calculated by alumina) of pseudo-boehmite powder into 45% of sodium hydroxide solution, controlling the reaction temperature at 130 ℃, and reacting for 25h, wherein Al is 2 O 3 /Na 2 O =0.50, noted as solution a;
(2) The concentration was 370g/l (in SiO) 2 Calculated) is added into the solution A, the temperature is controlled at 30 ℃, and the reaction is carried out for 19h, wherein SiO is 2 /Al 2 O 3 =0.8, note solution B;
(3) Dropwise adding 1mol/L ammonium dihydrogen phosphate solution into the solution B, controlling the pH =8.8 and the temperature at 30 ℃, and standing and aging for 0.8h;
(4) Washing with chemical water, filtering, adding chemical water, pulping, and recording as pulp C;
(5) Adding ZSM-5 molecular sieve dry powder into the slurry C, uniformly stirring, and recording as slurry D, wherein the ratio of the mass of the ZSM-5 molecular sieve dry powder to the dry basis mass of the silicon-aluminum matrix obtained in the step (4) is 4:6;
(5) And (3) spray-drying the slurry D at 300 ℃, and recording as a catalyst Cat-4 for preparing the low-carbon olefin by catalytic cracking of the waste plastic.
In the prepared catalyst Cat-4, the ZSM-5 molecular sieve accounts for about 40 percent of the mass of the catalyst, and SiO 2 The mass of the silicon-containing substance accounted for about 19% of the mass of the catalyst, al 2 O 3 The mass of the aluminum-containing material accounted for about 36% of the mass of the catalyst, and the balance about phosphorus pentoxide5％。
Example 5:
(1) Adding (calculated by alumina) 40% of pseudo-boehmite powder into 50% of sodium hydroxide solution, controlling the reaction temperature at 140 ℃, and reacting for 34h, wherein Al is 2 O 3 /Na 2 O =0.67, noted as solution a;
(2) The concentration was 400g/l (in SiO) 2 Meter) is added into the solution A, the temperature is controlled at 50 ℃, the reaction is carried out for 20h, wherein SiO is carried out 2 /Al 2 O 3 =1.0, note solution B;
(3) Dropwise adding 1mol/L ammonium dihydrogen phosphate solution into the solution B, controlling the pH =8.6 and the temperature at 23 ℃, and statically aging for 0.7h;
(4) Washing with chemical water, filtering, adding chemical water, pulping, and recording as pulp C;
(5) Adding ZSM-5 molecular sieve dry powder into the slurry C, uniformly stirring, and recording as slurry D, wherein the ratio of the mass of the ZSM-5 molecular sieve dry powder to the dry-basis mass of the silicon-aluminum matrix obtained in the step (4) is 4:6;
(5) And (3) spray-drying the slurry D at 320 ℃, and recording as a catalyst Cat-5 for preparing the low-carbon olefin by catalytic cracking of the waste plastic.
In the prepared catalyst Cat-5, the ZSM-5 molecular sieve accounts for about 40 percent of the mass of the catalyst, and SiO 2 The mass of the silicon-containing substance accounted for about 22% of the mass of the catalyst, al 2 O 3 The mass of the aluminum-containing material accounted for about 35% of the mass of the catalyst, with the remainder being about 3% of the phosphorus pentoxide.
Comparative example 1:
(1) 10g of molecular sieve (Si/Al molar ratio 32) with MFI configuration were dissolved in 200ml of NaOH solution (1 mol/L) and treated in a thermostatic water bath at 80 ℃ for 1 hour
(2) Dissolving 5g CTAB in 50ml of distilled water, heating, and stirring for 30 minutes to clarify the solution; taking slurry of the alkali-treated MFI molecular sieve as a silica-alumina source, slowly adding the slurry into a CTAB solution, stirring for 2 hours to fully and uniformly mix the solution, wherein the molar ratio of raw materials is SiO2: CTAB: A12O3: H2O =1:0.1:0.03:60, adding a solvent to the mixture;
(3) Adjusting the pH value of the solution to 10.5, and transferring the solution to a synthesis kettle with a polytetrafluoroethylene lining; the MCM-41 molecular sieve with the micro-mesoporous composite pore structure is prepared by the steps of carrying out commercialization for 24 hours at 110 ℃, washing and drying;
(4) Mixing the molecular sieve and a binder, molding, and roasting at 50 ℃ for 5 hours, wherein the binder is alumina; using ammonium nitrate as an exchanger, performing ion exchange on the molded sample, drying, and roasting at 560 ℃ for 2 hours to prepare a hydrogen type molecular sieve sample;
(5) Respectively taking zinc nitrate and phosphoric acid as precursors of zinc oxide and phosphorus oxide, introducing the zinc oxide and the phosphorus oxide into the hydrogen type molecular sieve sample by an impregnation method, drying, and roasting at 540 ℃ for 2 hours to obtain a finished catalyst, which is recorded as Cat-6.
The pore size distribution of Cat-1 and Cat-3 catalysts is shown in FIG. 1. The catalyst shown in FIG. 1Of a silicon-aluminium substrateThe mesoporous distribution diagram shows that the catalyst has two kinds of mesopores with the pore diameters of about 10nm and between 30 nm and 40 nm. The ordinate "dV/dlogW" in fig. 1 represents the differential value of the pore volume versus the pore diameter.
Aging of the catalyst: the prepared 6 catalysts are subjected to hydrothermal treatment for 17 hours at 800 ℃ under the condition of 100 percent of water vapor for later use.
Evaluation of catalyst: evaluation of the catalyst the evaluation was carried out on a FFB fixed fluidized bed. The raw materials are mixed plastic particles, and the specific proportion is PE: PP: PS =5, reaction temperature 500 ℃, catalyst/feedstock ratio 9. The evaluation results are shown in Table 1.
TABLE 1 evaluation results of catalysts
Catalyst and process for preparing same Cat-1 Cat-2 Cat-3 Cat-4 Cat-5 Cat-6
Yield of liquefied gas 65.1 63.4 61.5 60.2 59.6 32.6
Ethylene yield 5.4 5.2 5.1 5.0 4.9 2.7
Propylene yield 24.1 23.5 22.8 22.3 22.1 12.1
Total butene yield 22.0 21.4 20.8 20.3 20.1 11.0
Gasoline yield 18.1 19.2 20.1 22.5 23.7 36.7
Gasoline octane number (RON) 92 92 91 90 90 90
Coke selectivity 2.6 2.5 2.1 2.1 2.2 5.1

Claims (12)

1. The catalyst comprises a silicon-aluminum substrate and a molecular sieve, wherein the silicon-aluminum substrate comprises a silicon-containing substance, a phosphorus oxide and an aluminum-containing substance, and SiO is used as SiO 2 The mass of the silicon-containing substance accounts for 10 to 40wt% of the mass of the catalyst, and Al is used 2 O 3 The mass of the aluminum-containing substance accounts for 30 to 60wt% of the mass of the catalyst, and the mass is P 2 O 5 The mass of the phosphorus oxide accounts for 1.5 to 7.0wt percent of the mass of the catalyst, and the hole of the silicon-aluminum substrateThe volume is 0.8 to 1.3cm 3 Per g, the specific surface area is 380 to 550m 2 The pore size distribution of the silicon-aluminum matrix is 5-200nm, the pore size of 5-20nm accounts for 20-40%, and the pore size of 20-200nm accounts for 60-80%; the molecular sieve is a ZSM-5 molecular sieve or/and a ZSM-11 molecular sieve, and accounts for 10 to 40wt% of the mass of the catalyst;
the preparation method of the catalyst comprises the following steps:
mixing solution A obtained by mixing pseudo-boehmite and alkali metal hydroxide solution with silicate to obtain solution B, wherein SiO in the silicate in the mixed solution B 2 With Al in pseudo-boehmite 2 O 3 The mass ratio of the substances is SiO 2 /Al 2 O 3 =（0.05~2）：1；
Adding an ammonium dihydrogen phosphate solution into the solution B, adjusting the pH to be less than 10, and standing to generate a precipitate in the solution B;
filtering and washing the solution B containing the precipitate, wherein a filter cake is a silicon-aluminum matrix material;
mixing the silicon-aluminum substrate and the molecular sieve in water to obtain slurry C; the molecular sieve is a ZSM-5 molecular sieve or/and a ZSM-11 molecular sieve;
the slurry C was spray dried to obtain the final catalyst.
2. Use according to claim 1, characterized in that in the mixed solution B, siO is contained in the silicate 2 With Al in pseudo-boehmite 2 O 3 The mass ratio of the substances is SiO 2 /Al 2 O 3 =（0.25~1）：1。
3. Use according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide and the amounts of pseudoboehmite and sodium hydroxide are: al (Al) 2 O 3 /Na 2 The mass ratio of O is 0.1 to 0.9.
4. Use according to any one of claims 1 to 3, characterized in that the reaction temperature of the pseudoboehmite with the sodium hydroxide solution is controlled within the range of 80 ℃ to 140 ℃.
5. Use according to any one of claims 1 to 3, characterized in that the mass ratio of silicon oxide to alkali metal oxide in the silicate is 3.0 to 3.5.
6. Use according to any one of claims 1 to 3, characterized in that solution A is mixed with sodium silicate at a temperature of 20 to 50 ℃.
7. The application of the silicon-aluminum composite material as claimed in claim 1, wherein the addition amount of the molecular sieve is controlled in a ratio of the mass of the molecular sieve dry powder to the dry mass of the silicon-aluminum matrix within 1 to 9-4.
8. The use according to claim 1, wherein the slurry C is spray-dried at a temperature of 260 to 320 ℃.
9. The use according to claim 1, characterized in that ammonium dihydrogen phosphate solution is added to the solution B and the pH is adjusted to between 6.0 and 9.0.
10. Use according to claim 3, characterized in that Al 2 O 3 /Na 2 The mass ratio of O is 0.13 to 1 to 0.7.
11. Use according to claim 4, wherein the reaction time of the pseudoboehmite with the sodium hydroxide solution is between 5 and 40h.
12. The use according to claim 6, wherein the solution A is mixed with sodium silicate at a temperature of 20 to 50 ℃ for 15 to 20 hours.
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