CN116851030A - Novel catalyst, preparation method thereof and application thereof in reaction for preparing low-carbon olefin by directly converting waste plastics - Google Patents

Novel catalyst, preparation method thereof and application thereof in reaction for preparing low-carbon olefin by directly converting waste plastics Download PDF

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Publication number
CN116851030A
CN116851030A CN202210314372.6A CN202210314372A CN116851030A CN 116851030 A CN116851030 A CN 116851030A CN 202210314372 A CN202210314372 A CN 202210314372A CN 116851030 A CN116851030 A CN 116851030A
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molecular sieve
oxide
sba
novel catalyst
zsm
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刘红梅
王定博
亢宇
江珊
刘东兵
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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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
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-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
    • B01J29/40—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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of catalysts and the field of polymer material recycling, and discloses a novel catalyst, a preparation method thereof and application thereof in a reaction for preparing low-carbon olefin by directly converting waste plastics. The novel catalyst comprises a ZSM-5 molecular sieve, an SBA-16 all-silicon mesoporous molecular sieve, a first modified oxide and a second modified oxide, wherein the content of the ZSM-5 molecular sieve is 35-65 wt% based on the total weight of the novel catalyst, the content of the SBA-16 all-silicon mesoporous molecular sieve is 26-52.5 wt%, the content of the first modified oxide is 0.5-8 wt%, and the content of the second modified oxide is 1-12 wt%. The method solves the problem of recycling waste plastics and increases the yield of important chemical raw materials, namely low-carbon olefins.

Description

Novel catalyst, preparation method thereof and application thereof in reaction for preparing low-carbon olefin by directly converting waste plastics
Technical Field
The invention relates to the field of catalysts and the field of polymer material recycling, in particular to a novel catalyst, a preparation method thereof and application thereof in the reaction of directly converting waste plastics into low-carbon olefin.
Background
Since the advent of the 20 th century, plastic products have the characteristics of light weight, high strength, corrosion resistance, good chemical stability, convenient processing, beautiful appearance and practicability, and are widely applied to various fields in the world. However, plastics are difficult to degrade naturally, and conventional landfill techniques, although they are low in investment and simple to operate, can encroach on a large amount of land, causing land pollution. Although the incineration technology can realize the reduction requirement and recover part of energy, the process is easy to release a large amount of hydrocarbons, nitrides, sulfides and highly toxic substances, which directly threatens the health of human beings and ecological environment. Therefore, the recovery and high-value utilization of waste plastics are widely regarded as a measure for saving energy and protecting environment in all countries of the world. The waste plastic recycling method mainly comprises the technologies of classified recycling, monomer raw material preparation, clean fuel oil production, power generation and the like.
The plastic industry in China is one of the pillar industries of national economy, and China currently steps into the line of the plastic China in the world. Under the policy background of new plastic limiting command, sharp reduction of import quantity, garbage classification and the like, waste plastic recycling enterprises in China are gradually getting rid of old roads which are expanded widely before, and the industrial layout is gradually inspected with green development. Continuously and deeply cooperates with environmental protection and environmental sanitation enterprises to gradually realize the aims of green, low carbon and cyclic development. The large-scale waste plastic recycling enterprises in standard operation gradually classify the recycled waste plastic further finely, continuously develop and apply new technologies and new products of the waste plastic, gradually widen the application field of the waste plastic and improve the added value of the regenerated plastic products. In the prior art, the chemical recycling scheme of waste plastics is mainly waste plastic cracking technology. Waste plastic pyrolysis includes three basic methods, namely: thermal cracking (one-stage process), catalytic cracking (one-stage process) and thermal cracking-catalytic modification (two-stage process). The earliest waste plastic cracking technology developed was thermal cracking technology. The technology refers to a thermal conversion process of performing thermochemical decomposition reaction under the condition of high Wen Jue oxygen to convert macromolecular organic matters in waste plastic products into substances such as liquid matters with small molecular mass, fuel gas, coke and the like. The reaction temperature of the process is generally controlled between 350 and 900 ℃. If the catalyst is added in the thermal cracking process, the catalytic thermal cracking technology is adopted, so that the cracking temperature can be reduced, and the product performance can be improved. The improvement of thermal cracking-catalytic modification method is that after waste plastics are thermally cracked, the catalyst is used to make catalytic modification on the cracked gas.
The pyrolysis technology has wide flexibility in waste plastic treatment and good energy recovery, and is one of waste plastic treatment technologies with wide application prospects. In the prior art, the products produced by the one-step thermal cracking method and the one-step catalytic cracking method are mainly fuel oil, and only a small amount of low-carbon olefin (ethylene, propylene and butylene) can be obtained. If a large amount of low-carbon olefins are required, a two-stage process using a thermal cracking-catalytic reforming process is required. It is therefore an important research direction for plastic waste treatment to explore a new chemical recycling process to produce a clean and high quality end product.
Disclosure of Invention
The invention aims to provide a novel catalyst, a preparation method thereof and application thereof in the reaction of directly converting waste plastics into low-carbon olefin, aiming at the current problem that the content of the low-carbon olefin in the existing waste plastics catalytic cracking reaction product is low. The method solves the problem of recycling waste plastics and increases the yield of important chemical raw materials, namely low-carbon olefins.
In order to achieve the above object, a first aspect of the present invention provides a novel catalyst, wherein the novel catalyst comprises a ZSM-5 molecular sieve, a SBA-16 all-silica mesoporous molecular sieve, a first modified oxide and a second modified oxide, and the content of the ZSM-5 molecular sieve is 35 to 65 wt%, the content of the SBA-16 all-silica mesoporous molecular sieve is 26 to 52.5 wt%, the content of the first modified oxide is 0.5 to 8 wt%, and the content of the second modified oxide is 1 to 12 wt%, based on the total weight of the novel catalyst.
The second aspect of the present invention provides a preparation method of the novel catalyst, wherein the preparation method comprises the following steps:
mixing a ZSM-5 molecular sieve and an SBA-16 all-silicon mesoporous molecular sieve with the aqueous solution of the modifying component and performing contact reaction; then the novel catalyst is obtained through water removal, drying and roasting treatment;
wherein the aqueous modifying component solution comprises an acid, a metal salt and water; the acid is phosphoric acid and/or boric acid, and the metal salt is selected from nitrate of one or more of magnesium, calcium, strontium, barium, zinc, copper, cobalt, cerium, lanthanum and zirconium, preferably one or more of calcium nitrate, barium nitrate and magnesium nitrate hexahydrate.
The third aspect of the invention provides an application of the novel catalyst in a reaction for preparing low-carbon olefin by directly converting waste plastics.
Through the technical scheme, compared with the prior art, the technical scheme provided by the invention has the following advantages:
(1) The novel catalyst provided by the invention has the advantages of easily available raw materials, simple preparation method and process, easily controlled conditions and good product repeatability.
(2) The novel catalyst provided by the invention comprises an acidic zeolite molecular sieve and a large-aperture mesoporous material, has stable structure and good high temperature resistance, and is beneficial to the diffusion of raw materials and product molecules in the cracking reaction process.
(3) The novel catalyst provided by the invention can be used for converting waste plastics into low-carbon olefin in one step when being used for the reaction of preparing low-carbon olefin by directly converting waste plastics, and is a novel method for chemical recycling of waste plastics. Solves the problem of recycling waste plastics, increases the yield of important chemical raw materials, namely low-carbon olefin, and has good economic benefit.
(4) The novel catalyst provided by the invention is used for the reaction of preparing the low-carbon olefin by directly converting waste plastics, and has the advantages of mild process conditions, easiness in operation and low requirements on reaction devices.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a small angle X-ray diffraction (XRD) pattern of novel catalyst A of example 1;
fig. 2 is a wide-angle X-ray diffraction (XRD) pattern of novel catalyst a of example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a novel catalyst, wherein the novel catalyst comprises a ZSM-5 molecular sieve, a SBA-16 all-silica mesoporous molecular sieve, a first modified oxide and a second modified oxide, and the content of the ZSM-5 molecular sieve is 35 to 65 wt%, the content of the SBA-16 all-silica mesoporous molecular sieve is 26 to 52.5 wt%, the content of the first modified oxide is 0.5 to 8 wt%, and the content of the second modified oxide is 1 to 12 wt%, based on the total weight of the novel catalyst.
The inventors of the present invention found that: the cracking catalysts disclosed in the prior art have microporous zeolite molecular sieves (including ZSM-5, ZSM-11, ZSM-35 or ZRP) as the main components. The microporous molecular sieve has ordered and stable structure, but has narrow pore size, typically between 0.4-0.7 nm. The molecular weight of the waste plastic product is larger, and the molecular chain is longer. In the cracking reaction process of waste plastic products, reactant molecules and product molecules with larger sizes are difficult to diffuse between narrow pore channels, so that the contact between the reactant and an active center is influenced, and side reactions such as deep dehydrogenation and the like are easy to occur. The SBA-16 all-silicon mesoporous molecular sieve has the structural advantage of large specific surface area and large pore volume and the performance advantage of high temperature resistance. However, the silica surface having a basic skeleton structure composed of silicon and oxygen does not contain a functional group, and is inferior in activity in cleavage reaction. The inventor of the invention finds that if the structural advantage of the all-silicon mesoporous inorganic material and the surface acid center of the zeolite molecular sieve are comprehensively utilized when the waste plastic cracking catalyst is developed and researched, a certain amount of SBA-16 all-silicon mesoporous molecular sieve and ZSM-5 zeolite molecular sieve with higher silicon aluminum mole ratio are mixed and modified, and the catalyst is used as a main component of the catalyst for the waste plastic cracking reaction, so that the activity of the cracking catalyst can be effectively improved, and the selectivity of low-carbon olefin can be increased.
According to the invention, the ZSM-5 molecular sieve framework structure is fixed, the framework of the ZSM-5 molecular sieve is composed of two crossed pore canal systems, the straight cylindrical pore canal is elliptic, and the long axis isShort axis is->The other is a Z-shaped transverse duct with a cross section close to a circle and an aperture of +.>Compared with ZSM-5 molecular sieve with narrow pore canal, the average pore diameter of SBA-16 all-silicon mesoporous molecular sieve is between 5 and 8nm, and the specific surface area is higher than 600m 2 And/g. Proper amount of SBA-16 full-silicon mesoporous molecular sieve is mixed with ZSM-5 with high silicon-aluminum ratio, which is favorable for smooth diffusion of reactant molecules and product molecules with larger molecular volume and can effectively avoid side reaction.
According to the present invention, preferably, the content of the ZSM-5 molecular sieve is 40 to 60 wt%, the content of the SBA-16 all-silicon mesoporous molecular sieve is 32 to 50 wt%, the content of the first modified oxide is 1 to 6 wt%, and the content of the second modified oxide is 2 to 9 wt%, based on the total weight of the novel catalyst; more preferably, the ZSM-5 molecular sieve is 45 to 55 wt%, the SBA-16 all-silicon mesoporous molecular sieve is 35 to 46 wt%, the first modified oxide is 1.5 to 3.5 wt%, and the second modified oxide is 3.5 to 8.5 wt%, based on the total weight of the novel catalyst; still more preferably, the ZSM-5 molecular sieve is present in an amount of from 46.7 to 54.6 wt%, the SBA-16 all-silica mesoporous molecular sieve is present in an amount of from 35.7 to 45.9 wt%, the first modified oxide is present in an amount of from 1.6 to 3.5 wt%, and the second modified oxide is present in an amount of from 3.9 to 8.1 wt%, based on the total weight of the novel catalyst. In the invention, the prepared cracking catalyst has better catalytic activity and higher low-carbon olefin selectivity when being used for the reaction of preparing the low-carbon olefin by directly converting waste plastics by adopting the content of the specific components.
According to the invention, the inventor adopts a mixture of ZSM-5 molecular sieve with a silicon aluminum molar ratio (Si/Al) of 50-500 and SBA-16 all-silicon mesoporous molecular sieve as main active components, and introduces oxide as a modifying component, so that the catalyst activity and the low-carbon olefin selectivity can be improved. Preferably, when the mole ratio of silicon to aluminum of the ZSM-5 zeolite molecular sieve is 100-300, the catalyst activity and the low-carbon olefin selectivity can be obviously improved.
According to the invention, the first oxide may be one or more of a non-metal oxide or a metalloid oxide, preferably one or more of boron oxide or phosphorus pentoxide.
According to the present invention, the second oxide is selected from one or more of alkaline earth metal oxides, transition metal oxides, and rare earth metal oxides; preferably, the second oxide is selected from one or more of magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, copper oxide, cobalt oxide, cerium oxide, lanthanum oxide, and zirconium dioxide.
According to the invention, the specific surface area of the SBA-16 all-silicon mesoporous molecular sieve is 600-1000m 2 And/g, pore volume of 0.4-1.0mLg, with an average pore size of 5-8nm; preferably, the specific surface area of the SBA-16 all-silicon mesoporous molecular sieve is 700-900m 2 Per gram, the pore volume is 0.5-0.8mL/g, and the average pore diameter is 5.5-7.5nm; more preferably, the specific surface area of the SBA-16 all-silicon mesoporous molecular sieve is 749-853m 2 Per gram, the pore volume is 0.6-0.7mL/g, and the average pore diameter is 6.0-7.0nm. In the invention, the SBA-16 all-silicon mesoporous molecular sieve with the specific parameters is adopted, so that the prepared cracking catalyst has better catalytic activity and higher selectivity when being used for the reaction of preparing the low-carbon olefin by directly converting waste plastics.
According to the invention, the preparation method of the SBA-16 all-silicon mesoporous molecular sieve comprises the following steps:
(1) Mixing a template agent, an acidic aqueous solution, n-butanol and chitosan to obtain a mixture;
(2) The mixture is contacted with a silicon source for reaction, and then is subjected to standing crystallization and separation treatment to obtain a solid product;
(3) And washing, drying and roasting the solid product to obtain the SBA-16 all-silicon mesoporous molecular sieve.
According to the invention, the templating agent may be an amphoteric triblock polymer, preferably F127 (polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, formula EO) 106 PO 70 EO 106 )。
According to the present invention, the acidic aqueous solution may be an aqueous solution of an inorganic acid, preferably one or more of dilute hydrochloric acid or dilute nitric acid, more preferably dilute hydrochloric acid; the concentration of the acidic aqueous solution may be 0.2 to 10%, preferably 0.5 to 3%.
According to the present invention, the silicon source may be an organic silicon-containing compound or an inorganic silicon-containing compound, preferably one or more of methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate, or silica sol, more preferably ethyl orthosilicate.
According to the invention, the templating agent: acidic aqueous solution: n-butanol: chitosan: the weight ratio of the silicon source may be 1: (10-200): (0.2-10): (0.05-1.0): (1-8), preferably 1: (20-100): (0.5-3): (0.1-0.5): (2-4).
According to the invention, the mixing conditions include: the stirring speed is 50-300r/min, the temperature is 20-60 ℃ and the time is 0.5-6h; preferably, the stirring speed is 150-250r/min, the temperature is 20-40 ℃ and the time is 0.5-3h.
According to the invention, the contacting may be carried out at a temperature of 50-150 ℃, preferably 80-120 ℃; the time is 3-40 hours, preferably 10-20 hours.
According to the invention, the conditions for the standing crystallization may be a temperature of 50-150 ℃, preferably 80-120 ℃; the time is 10-48 hours, preferably 16-30 hours.
And/or, the contacting conditions include: the temperature is 50-150 ℃ and the time is 3-40h;
and/or, the crystallization conditions include: the temperature is 50-150 ℃ and the time is 10-48h;
and/or, the roasting conditions include: the temperature is 400-700 ℃ and the time is 2-24h.
According to the present invention, there is no particular requirement for the solid-liquid two-phase separation process, and the separation methods may be those known in the art, including gravity filtration, pressure filtration, vacuum filtration or centrifugal filtration. Preferably, the separation process specifically includes: vacuum-pumping the bottom of the funnel by using a suction bottle or filtering by using a centrifugal filter.
According to the invention, the method of washing the solid product is not particularly required, for example: the solid product may be washed with deionized water, the volume ratio of deionized water to solid product may be 5-20, and the number of washes may be 2-8.
According to the invention, the drying conditions may be at a temperature of 80-150 ℃, preferably 100-130 ℃; the time is 2-30 hours, preferably 5-20 hours.
According to the invention, the conditions of the calcination may be temperatures of 400-700 ℃, preferably 500-600 ℃; the time is 2-24 hours, preferably 4-12 hours.
The second aspect of the present invention provides a preparation method of the novel catalyst, wherein the preparation method comprises the following steps:
mixing a ZSM-5 molecular sieve and an SBA-16 all-silicon mesoporous molecular sieve with the aqueous solution of the modifying component and performing contact reaction; then the novel catalyst is obtained through water removal, drying and roasting treatment;
wherein the aqueous modifying component solution comprises an acid, a metal salt and water; the acid is phosphoric acid and/or boric acid, and the metal salt is selected from nitrate of one or more of magnesium, calcium, strontium, barium, zinc, copper, cobalt, cerium, lanthanum and zirconium, preferably one or more of calcium nitrate, barium nitrate and magnesium nitrate hexahydrate.
According to the invention, the aqueous solution of the modifying component may have a mass concentration of 1 to 20%, preferably 2 to 10%.
According to the invention, the weight ratio of the ZSM-5 molecular sieve, the SBA-16 all-silicon mesoporous molecular sieve and the modifying component aqueous solution is 1: (0.3-1.6): (3-30), preferably 1: (0.5-1.3): (6-20).
According to the invention, the conditions of the contact reaction include: the temperature is 10-100deg.C, preferably 30-80deg.C; the time is 0.5-50h, preferably 2-20h. Preferably, in order to achieve better mixing effect, the mixing efficiency can be improved by rapid stirring or by means of ultrasonic means in the process of mixing the ZSM-5 molecular sieve, the SBA-16 all-silicon mesoporous molecular sieve and the aqueous solution of the modifying component.
The water removal method according to the present invention is not particularly limited, and may be a water removal method known in the art, such as: evaporating to remove water by using a rotary evaporator or adopting a heating and stirring method to remove water.
According to the invention, the drying conditions include: the temperature is 60-150deg.C, preferably 80-130deg.C; the time is 1-30 hours, preferably 3-20 hours.
According to the invention, the conditions of the calcination include: the temperature is 400-700 ℃, preferably 500-600 ℃; the time is 2-20h, preferably 3-10h.
The third aspect of the invention provides an application of the novel catalyst in a reaction for preparing low-carbon olefin by directly converting waste plastics.
According to the invention, the application comprises: the plastic powder is contacted with the novel catalyst for reaction.
And/or, the contacting conditions include: the temperature is 420-580 ℃, the pressure is 0.01-1MPa, and the contact time is 0.5-12h;
and/or the weight ratio of the novel catalyst to the amount of the waste plastic powder is 1: (0.5-50).
In the present invention, the conditions under which the waste plastic powder is contacted with the novel catalyst include: the temperature of contact may be 420-580 ℃, preferably 450-540 ℃; the contact pressure may be 0.01-1.0Mpa, preferably 0.05-0.5Mpa; the contact time may be 0.5 to 12 hours, preferably 1 to 5 hours; the weight ratio of the novel catalyst to the waste plastic powder can be 1:0.5 to 50, preferably 1:2-30.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
small angle XRD testing of the samples was performed on a high power, rotary target X-ray diffractometer, D8ADVANCE, BRUKER AXS, germany, scan range: 0.5-10 deg..
Wide angle XRD testing of the samples was performed on an X' Pert MPD X-ray powder diffractometer, philips company, netherlands, cu ka target, scan range 2θ=5-90 °.
The pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. The sample was vacuum degassed at 350 ℃ for 4 hours prior to measurement, the specific surface area of the sample was calculated using the BET method, and the pore volume was calculated using the BJH model.
Elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
The rotary evaporator is manufactured by IKA corporation of Germany and has the model RV10digital.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
The ZSM-5 molecular sieves of varying silica to alumina ratios used in the examples and comparative examples were purchased from south-open catalyst plants; the other reagents used in the examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
Example 1
(1) Preparation of SBA-16 all-silicon mesoporous molecular sieve
In a 1000ml round bottom flask, 10g of polyether F127, 20g of concentrated hydrochloric acid and 500ml of deionized water are added, mixed and stirred for 30 minutes at room temperature; continuously adding 15g of n-butanol and 2g of chitosan into the flask, and stirring for 1h; slowly adding 25g of ethyl orthosilicate, heating to 100 ℃, stirring and reacting for 16 hours, and standing and crystallizing at 100 ℃ for 24 hours. After crystallization, filtering to obtain a white solid product, washing with deionized water for 8 times, drying in air at 120 ℃ for 10 hours, and roasting at 550 ℃ for 8 hours to obtain the SBA-16 mesoporous molecular sieve A.
The specific surface area of the SBA-16 all-silicon mesoporous molecular sieve A is 794m 2 Per gram, pore volume of 0.65cm 3 And/g, average pore diameter of 6.5nm.
(2) Preparation of novel catalysts
An aqueous solution of the modified component was prepared by dissolving 3.6g of phosphoric acid and 17.6g of calcium nitrate in 400g of distilled water. 51g of ZSM-5 molecular sieve (Si/Al=200) and 42g of SBA-16 all-silicon mesoporous molecular sieve A were added to the above-mentioned aqueous solution of the modified component, after stirring at 60℃for 5 hours, the water was removed by using a rotary evaporator, and the solid product was dried at 110℃for 8 hours and then calcined at 550℃for 6 hours, to obtain a novel catalyst A.
Fig. 1 is a small angle XRD spectrum of catalyst a. The spectrogram shows that the sample has a strong diffraction signal corresponding to a (110) crystal face within the range of 2 theta = 0.5-1 degrees, which indicates that the SBA-16 all-silicon mesoporous molecular sieve still has a regular mesoporous pore structure after being prepared into a catalyst, and the basic structure of the mesoporous molecular sieve is not damaged in the catalyst preparation process.
Fig. 2 is a wide angle XRD spectrum of catalyst a. The spectrum shows that the x-ray diffraction angle of the sample is mainly: 2θ=8.0 °, 8.8 °, 14.8 °, 23.0 °, and 24.0 °. The five diffraction signals are consistent with the diffraction patterns of the ZSM-5 molecular sieve, which shows that the ZSM-5 molecular sieve in the catalyst A still maintains the typical MFI crystal phase structure, and the basic structure of the ZSM-5 molecular sieve is not damaged in the preparation process of the catalyst. The diffraction signal corresponding to the modified oxide did not appear in the wide angle XRD pattern, indicating that the modified component was in a uniformly dispersed state on the catalyst.
The specific surface area, pore volume and composition of catalyst a are listed in table 1.
(3) Evaluation of reaction performance of preparing low-carbon olefin by directly converting waste plastics
The catalytic cracking reaction performance of the catalyst, methyl tertiary butyl ether, was evaluated on a fixed bed reactor. Catalyst loading 10.0 g, polypropylene waste plastic loading 60.0g, reaction temperature 500 ℃, reaction pressure 0.1MPa, reaction time 2 hours, cooling product, gas-liquid separation, gas composition using Al 2 O 3 -agilent 6890 gas chromatograph analysis of S capillary chromatography column and hydrogen flame detector (FID), quantitative analysis with correction factor using temperature programming; the liquid composition was analyzed with an Agilent 6890 gas chromatograph equipped with a PONA column. The reaction results are shown in Table 2.
Example 2
(1) Preparation of SBA-16 all-silicon mesoporous molecular sieve
10g of polyether F127 and 200g of 3% dilute hydrochloric acid are added into a 1000ml round-bottom flask, and mixed and stirred for 30 minutes at room temperature; continuously adding 5g of n-butanol and 1g of chitosan into the flask, and stirring for 1h; slowly adding 20g of ethyl orthosilicate, heating to 80 ℃, stirring and reacting for 20h, and standing and crystallizing at 80 ℃ for 30h. After crystallization, filtering to obtain a white solid product, washing the white solid product with deionized water for 6 times, drying the white solid product in air at 100 ℃ for 20 hours, and roasting the white solid product at 500 ℃ for 12 hours to obtain the SBA-16 mesoporous molecular sieve B.
The specific surface area of the SBA-16 mesoporous molecular sieve B is 853m 2 Per gram, pore volume of 0.7cm 3 And/g, average pore diameter of 6.0nm.
(2) Preparation of novel catalysts
2.8g of boric acid and 50.8g of magnesium nitrate hexahydrate were dissolved in 600g of distilled water to prepare an aqueous modified component solution. 55g of ZSM-5 molecular sieve (Si/Al=300) and 36g of SBA-16 all-silicon mesoporous molecular sieve B are added into the aqueous solution of the modified component, after stirring for 2 hours at 80 ℃, the water is removed by using a rotary evaporator, and the solid product is dried for 3 hours at 130 ℃ and then baked for 3 hours at 600 ℃ to obtain the novel catalyst B.
The specific surface area, pore volume and composition of catalyst B are listed in table 1.
The reaction performance of catalyst B was tested according to the evaluation method of the reaction performance of the direct conversion of waste plastics to light olefins of step (3) in example 1, and the evaluation results are shown in table 2.
Example 3
(1) Preparation of SBA-16 all-silicon mesoporous molecular sieve
10g of polyether F127 and 200g of 0.5% dilute hydrochloric acid are added into a 2000ml round-bottom flask, and mixed and stirred for 30 minutes at room temperature; continuously adding 30g of n-butanol and 5g of chitosan into the flask, and stirring for 1h; slowly adding 40g of tetraethoxysilane, heating to 120 ℃, stirring and reacting for 10 hours, and standing and crystallizing at 120 ℃ for 16 hours. After crystallization, filtering to obtain a white solid product, washing with deionized water for 8 times, drying in the air at 130 ℃ for 5 hours, and roasting at 600 ℃ for 4 hours to obtain the SBA-16 mesoporous molecular sieve C.
The specific surface area of the SBA-16 mesoporous molecular sieve C is 749m 2 Per gram, pore volume of 0.6cm 3 And/g, average pore diameter of 7.0nm.
(2) Preparation of novel catalysts
An aqueous solution of the modified component was prepared by dissolving 4.8g of phosphoric acid and 6.7g of barium nitrate in 300g of distilled water. 47g of ZSM-5 molecular sieve (Si/Al=100) and 46g of SBA-16 all-silicon mesoporous molecular sieve C are added into the aqueous solution of the modified component, after stirring for 20 hours at 30 ℃, a rotary evaporator is used for removing water, and the solid product is dried for 20 hours at 80 ℃ and then baked for 10 hours at 500 ℃ to obtain the novel catalyst C.
The specific surface area, pore volume and composition of catalyst C are listed in table 1.
The reaction performance of the catalyst C was tested according to the evaluation method of the reaction performance of the waste plastics directly converted to light olefins in the step (3) of example 1, and the evaluation results are shown in Table 2.
Example 4
SBA-16 all-silicon mesoporous molecular sieve A was prepared according to the method of step (1) in example 1.
Novel catalyst D was prepared according to the procedure of step (2) in example 1. The preparation conditions are changed, and the specific process is as follows:
an aqueous solution of the modified component was prepared by dissolving 1.4g of phosphoric acid and 26.4g of calcium nitrate in 400g of distilled water. 40g of ZSM-5 molecular sieve (Si/Al=200) and 50g of SBA-16 all-silicon mesoporous molecular sieve A are added into the aqueous solution of the modified component, after stirring for 5 hours at 60 ℃, a rotary evaporator is used for removing water, and the solid product is dried for 8 hours at 110 ℃ and then baked for 6 hours at 550 ℃ to obtain the novel catalyst D.
The specific surface area, pore volume and composition of catalyst D are listed in table 1.
The reaction performance of catalyst D was tested according to the evaluation method of the reaction performance of the direct conversion of waste plastics to light olefins of step (3) in example 1, and the evaluation results are shown in table 2.
Example 5
SBA-16 all-silicon mesoporous molecular sieve B was prepared according to the method of step (1) in example 2.
Novel catalyst E was prepared according to the procedure of step (2) in example 2. The preparation conditions are changed, and the specific process is as follows:
an aqueous solution of the modified component was prepared by dissolving 10.6g of boric acid and 12.8g of magnesium nitrate hexahydrate in 600g of distilled water. 60g of ZSM-5 molecular sieve (Si/Al=100) and 32g of SBA-16 all-silicon mesoporous molecular sieve B are added into the aqueous solution of the modified component, after stirring for 2 hours at 80 ℃, the water is removed by using a rotary evaporator, and the solid product is dried for 3 hours at 130 ℃ and then baked for 3 hours at 600 ℃ to obtain the novel catalyst E.
The specific surface area, pore volume and composition of catalyst E are listed in Table 1.
The reaction performance of the catalyst E was tested according to the evaluation method of the reaction performance of the waste plastics directly converted to light olefins in the step (3) of example 1, and the evaluation results are shown in Table 2.
Example 6
SBA-16 all-silicon mesoporous molecular sieve A was prepared according to the method of step (1) in example 1.
Novel catalyst F was prepared according to the procedure of step (2) in example 1. The preparation conditions are changed, and the specific process is as follows:
an aqueous solution of the modified component was prepared by dissolving 0.7g of phosphoric acid and 35.2g of calcium nitrate in 400g of distilled water. 35g of ZSM-5 molecular sieve (Si/Al=200) and 52.5g of SBA-16 all-silicon mesoporous molecular sieve A are added into the aqueous solution of the modified component, after stirring for 5 hours at 60 ℃, the water is removed by using a rotary evaporator, and the solid product is dried for 8 hours at 110 ℃ and then baked for 6 hours at 550 ℃ to obtain the novel catalyst F.
The specific surface area, pore volume and composition of catalyst F are listed in Table 1.
The reaction performance of the catalyst F was tested according to the evaluation method of the reaction performance of the waste plastics directly converted to light olefins in the step (3) of example 1, and the evaluation results are shown in Table 2.
Example 7
SBA-16 all-silicon mesoporous molecular sieve B was prepared according to the method of step (1) in example 2.
Novel catalyst G was prepared according to the procedure of step (2) in example 2. The preparation conditions are changed, and the specific process is as follows:
an aqueous solution of the modified component was prepared by dissolving 14.1g of boric acid and 6.4g of magnesium nitrate hexahydrate in 600g of distilled water. 65G of ZSM-5 molecular sieve (Si/Al=100) and 26G of SBA-16 all-silicon mesoporous molecular sieve B are added into the aqueous solution of the modified component, after stirring for 2 hours at 80 ℃, the water is removed by using a rotary evaporator, and the solid product is dried for 3 hours at 130 ℃ and then baked for 3 hours at 600 ℃ to obtain the novel catalyst G.
The specific surface area, pore volume and composition of catalyst G are listed in table 1.
The reaction performance of catalyst G was tested according to the evaluation method of the reaction performance of the waste plastics directly converted to light olefins in step (3) of example 1, and the evaluation results are shown in table 2.
Comparative example 1
SBA-16 all-silicon mesoporous molecular sieve A was prepared according to the method of step (1) in example 1.
Novel catalyst D1 was prepared according to the procedure of step (2) in example 1. The preparation conditions are changed, and the specific process is as follows:
an aqueous solution of the modified component was prepared by dissolving 0.1g of phosphoric acid and 66.0g of zinc nitrate hexahydrate in 400g of distilled water. 16g of ZSM-5 molecular sieve (Si/Al=200) and 87g of SBA-16 all-silicon mesoporous molecular sieve A are added into the aqueous solution of the modified component, after stirring for 5 hours at 60 ℃, a rotary evaporator is used for removing water, and the solid product is dried for 8 hours at 110 ℃ and then baked for 6 hours at 550 ℃ to obtain the novel catalyst D1.
The specific surface area, pore volume and composition of catalyst D1 are listed in table 1.
Catalyst D1 was tested for its reactivity according to the method for evaluating the reactivity of the waste plastics directly converted to light olefins of step (3) of example 1, and the evaluation results are shown in Table 2.
Comparative example 2
SBA-16 all-silicon mesoporous molecular sieve B was prepared according to the method of step (1) in example 2.
Novel catalyst D2 was prepared according to the procedure of step (2) in example 2. The preparation conditions are changed, and the specific process is as follows:
24.8g of boric acid and 1.8g of copper nitrate hexahydrate were dissolved in 500g of distilled water to prepare an aqueous modified component solution. 74g of ZSM-5 molecular sieve (Si/Al=100) and 12g of SBA-16 all-silicon mesoporous molecular sieve B are added into the aqueous solution of the modified component, after stirring for 2 hours at 80 ℃, the water is removed by using a rotary evaporator, and the solid product is dried for 3 hours at 130 ℃ and then baked for 3 hours at 600 ℃ to obtain the novel catalyst D2.
The specific surface area, pore volume and composition of catalyst D2 are listed in table 1.
Catalyst D2 was tested for its reactivity according to the method for evaluating the reactivity of the waste plastics directly converted to light olefins of step (3) of example 1, and the evaluation results are shown in Table 2.
Comparative example 3
SBA-16 all-silicon mesoporous molecular sieve B was prepared according to the method of step (1) in example 2.
Novel catalyst D3 was prepared according to the procedure of step (2) in example 1. The preparation conditions are changed, and a ZSM-5 molecular sieve is not used, and the specific process is as follows:
an aqueous solution of the modified component was prepared by dissolving 3.6g of phosphoric acid and 17.6g of calcium nitrate in 400g of distilled water. 92g of SBA-16 full-silicon mesoporous molecular sieve B is added into the aqueous solution of the modified component, the mixture is stirred at 60 ℃ for 5 hours, then the water is removed by using a rotary evaporator, the solid product is dried at 110 ℃ for 8 hours, and then the solid product is baked at 550 ℃ for 6 hours, so that the novel catalyst D3 is obtained.
The specific surface area, pore volume and composition of catalyst D3 are listed in table 1.
Catalyst D3 was tested for its reactivity according to the method for evaluating the reactivity of the waste plastics directly converted to light olefins of step (3) of example 1, and the evaluation results are shown in Table 2.
Comparative example 4
Novel catalyst D4 was prepared according to the procedure of step (2) in example 1. The preparation conditions are changed, and the SBA-16 all-silicon mesoporous molecular sieve is not used, and the specific process is as follows:
an aqueous solution of the modified component was prepared by dissolving 3.6g of phosphoric acid and 17.6g of calcium nitrate in 400g of distilled water. 92g of ZSM-5 molecular sieve (Si/Al=200) was added to the above aqueous solution of the modifying component, after stirring at 60℃for 5 hours, the water was removed by using a rotary evaporator, and the solid product was dried at 110℃for 8 hours and then calcined at 550℃for 6 hours to give a novel catalyst D4.
The specific surface area, pore volume and composition of catalyst D4 are listed in table 1.
Catalyst D4 was tested for its reactivity according to the method for evaluating the reactivity of the waste plastics directly converted to light olefins of step (3) of example 1, and the evaluation results are shown in Table 2.
Comparative example 5
SBA-16 all-silicon mesoporous molecular sieve A was prepared according to the method of step (1) in example 1.
Novel catalyst D5 was prepared according to the procedure of step (2) in example 1. The preparation conditions are changed, and the first modification component is not added, and the specific process is as follows:
25.2g of calcium nitrate was dissolved in 400g of distilled water to prepare an aqueous modified component solution. 51g of ZSM-5 molecular sieve (Si/Al=200) and 42g of SBA-16 all-silicon mesoporous molecular sieve A were added to the above-mentioned aqueous solution of the modified component, after stirring at 60℃for 5 hours, the water was removed by using a rotary evaporator, and the solid product was dried at 110℃for 8 hours and then calcined at 550℃for 6 hours, to obtain a novel catalyst D5.
The specific surface area, pore volume and composition of catalyst D5 are listed in table 1.
Catalyst D5 was tested for its reactivity according to the method for evaluating the reactivity of the waste plastics directly converted to light olefins of step (3) of example 1, and the evaluation results are shown in Table 2.
Comparative example 6
SBA-16 all-silicon mesoporous molecular sieve B was prepared according to the method of step (1) in example 2.
Novel catalyst D6 was prepared according to the procedure of step (2) in example 1. The preparation conditions are changed, and a second modification component is not added, and the specific process is as follows:
11.9g of phosphoric acid was dissolved in 400g of distilled water to prepare an aqueous modified component solution. 51g of ZSM-5 molecular sieve (Si/Al=100) and 42g of SBA-16 all-silicon mesoporous molecular sieve B are added into the aqueous solution of the modified component, after stirring for 5 hours at 60 ℃, the water is removed by using a rotary evaporator, and the solid product is dried for 8 hours at 110 ℃ and then baked for 6 hours at 550 ℃ to obtain a novel catalyst D6.
The specific surface area, pore volume and composition of catalyst D6 are listed in table 1.
Catalyst D6 was tested for its reactivity according to the method for evaluating the reactivity of the waste plastics directly converted to light olefins of step (3) of example 1, and the evaluation results are shown in Table 2.
Comparative example 7
SBA-16 all-silicon mesoporous molecular sieve A was prepared according to the method of step (1) in example 1.
Novel catalyst D7 was prepared according to the procedure of step (2) in example 1. The preparation conditions are changed, and the first modified component and the second modified component are not added, and the specific process is as follows:
55g of ZSM-5 molecular sieve (Si/Al=200) and 45g of SBA-16 all-silicon mesoporous molecular sieve A are mixed with 400g of distilled water, after stirring for 5 hours at 60 ℃, the water is removed by using a rotary evaporator, and the solid product is dried for 8 hours at 110 ℃ and then baked for 6 hours at 550 ℃ to obtain a novel catalyst D7.
The specific surface area, pore volume and composition of catalyst D7 are listed in table 1.
Catalyst D7 was tested for its reactivity according to the method for evaluating the reactivity of the waste plastics directly converted to light olefins of step (3) of example 1, and the evaluation results are shown in Table 2.
Comparative example 8
SBA-16 all-silicon mesoporous molecular sieve A was prepared according to the method of step (1) in example 1.
Novel catalyst D8 was prepared according to the procedure of step (2) in example 1. Changing the preparation condition, changing the second modified oxide into sodium oxide, and the specific process is as follows:
an aqueous solution of the modified component was prepared by dissolving 3.6g of phosphoric acid and 16.5g of calcium nitrate in 400g of distilled water. 51g of ZSM-5 molecular sieve (Si/Al=200) and 42g of SBA-16 all-silicon mesoporous molecular sieve A were added to the above-mentioned aqueous solution of the modified component, after stirring at 60℃for 5 hours, the water was removed by using a rotary evaporator, and the solid product was dried at 110℃for 8 hours and then calcined at 550℃for 6 hours, to obtain a novel catalyst D8.
The specific surface area, pore volume and composition of catalyst D8 are listed in table 1.
Catalyst D8 was tested for its reactivity according to the method for evaluating the reactivity of the waste plastics directly converted to light olefins of step (3) of example 1, and the evaluation results are shown in Table 2.
TABLE 1
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TABLE 2
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From the results, the novel catalyst provided by the invention can directly catalyze and convert waste plastics to generate low-carbon olefin. The conversion rate of the waste plastics is 100 percent, and the yield of the low-carbon olefin is high.
In comparative example 1, the content of SBA-16 all-silica mesoporous molecular sieve was too high, the content of ZSM-5 molecular sieve was too low, and the content of the modifying component was not within the scope of the claims. Because of the small number of acid centers on the catalyst and insufficient activation sites in the reaction process, the raw material conversion rate is low and the low-carbon olefin yield is low.
In comparative example 2, the content of SBA-16 all-silica mesoporous molecular sieve was too low, the content of ZSM-5 molecular sieve was too high, and the content of the modifying component was not within the scope of the claims. The catalyst has low yield of low-carbon olefin due to less macroporous pore diameter and less diffusion resistance of reactant and product molecules in the reaction process.
In comparative example 3, the catalyst contained no ZSM-5 molecular sieve and only SBA-16 fully-silica mesoporous molecular sieve. Because the catalyst contains almost no acid center, the active sites are seriously lacking in the reaction process, so that the raw material conversion rate is very low, and the low-carbon olefin yield is low.
In comparative example 4, the catalyst contained no SBA-16 fully-silica mesoporous molecular sieve and only ZSM-5 molecular sieve. The catalyst contains almost no large pore diameter pore canal, and the diffusion of reactant and product molecules is seriously blocked in the reaction process, so that the yield of the low-carbon olefin is lower.
In comparative example 5, the catalyst contained no first modified oxide and only the second modified oxide, resulting in a lower yield of low-carbon olefin.
In comparative example 6, the catalyst contained no second modified oxide and only the first modified oxide, resulting in lower yields of lower olefins.
In comparative example 7, the catalyst contained no modified oxide, resulting in lower yields of lower olefins.
In comparative example 8, the second modified oxide specifically defined in the present invention was not used, but sodium oxide was used, and the low-carbon olefin yield was low due to the low modifying effect of sodium oxide of the same weight.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (11)

1. The novel catalyst is characterized by comprising a ZSM-5 molecular sieve, an SBA-16 all-silicon mesoporous molecular sieve, a first modified oxide and a second modified oxide, wherein the content of the ZSM-5 molecular sieve is 35-65 wt%, the content of the SBA-16 all-silicon mesoporous molecular sieve is 26-52.5 wt%, the content of the first modified oxide is 0.5-8 wt%, and the content of the second modified oxide is 1-12 wt% based on the total weight of the novel catalyst.
2. The novel catalyst of claim 1, wherein the ZSM-5 molecular sieve is present in an amount of 40-60 wt%, the SBA-16 all-silicon mesoporous molecular sieve is present in an amount of 32-50 wt%, the first modified oxide is present in an amount of 1-6 wt%, and the second modified oxide is present in an amount of 2-9 wt%, based on the total weight of the novel catalyst;
preferably, the ZSM-5 molecular sieve is 45-55 wt%, the SBA-16 all-silicon mesoporous molecular sieve is 35-46 wt%, the first modified oxide is 1.5-3.5 wt% and the second modified oxide is 3.5-8.5 wt%, based on the total weight of the novel catalyst.
3. The novel catalyst according to claim 1 or 2, wherein the ZSM-5 molecular sieve has a molar Si/Al ratio of 50-500, preferably 100-300.
4. The novel catalyst according to claim 1 or 2, wherein the first oxide is selected from one or more of a non-metal oxide or a metalloid oxide;
preferably, the first oxide is selected from one or more of boron oxide and phosphorus pentoxide;
and/or the second oxide is selected from one or more of alkaline earth metal oxide, transition metal oxide and rare earth metal oxide;
preferably, the second oxide is selected from one or more of magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, copper oxide, cobalt oxide, cerium oxide, lanthanum oxide, and zirconium dioxide.
5. The novel catalyst according to claim 1 or 2, wherein the specific surface area of the SBA-16 all-silicon mesoporous molecular sieve is 600-1000m 2 Per gram, the pore volume is 0.4-1.0mL/g, and the average pore diameter is 5-8nm;
preferably, the specific surface area of the SBA-16 all-silicon mesoporous molecular sieve is 700-900m 2 Per gram, the pore volume is 0.5-0.8mL/g, and the average pore diameter is 5.5-7.5nm;
more preferably, the specific surface area of the SBA-16 all-silicon mesoporous molecular sieve is 749-853m 2 Per gram, the pore volume is 0.6-0.7mL/g, and the average pore diameter is 6.0-7.0nm.
6. The novel catalyst according to claim 1 or 5, wherein the preparation method of the SBA-16 all-silicon mesoporous molecular sieve comprises the following steps:
(1) Mixing a template agent, an acidic aqueous solution, n-butanol and chitosan to obtain a mixture;
(2) The mixture is contacted with a silicon source for reaction, and then is subjected to standing, crystallization and separation treatment to obtain a solid product;
(3) And washing, drying and roasting the solid product to obtain the SBA-16 all-silicon mesoporous molecular sieve.
7. The novel catalyst of claim 6, wherein the templating agent: acidic aqueous solution: n-butanol: chitosan: the weight ratio of the silicon source may be 1: (10-200): (0.2-10): (0.05-1.0): (1-8);
and/or, the contacting conditions include: the temperature is 50-150 ℃ and the time is 3-40h;
and/or, the crystallization conditions include: the temperature is 50-150 ℃ and the time is 10-48h;
and/or, the roasting conditions include: the temperature is 400-700 ℃ and the time is 2-24h.
8. A process for preparing a novel catalyst as claimed in any one of claims 1 to 7, comprising:
mixing a ZSM-5 molecular sieve and an SBA-16 all-silicon mesoporous molecular sieve with the aqueous solution of the modifying component and performing contact reaction; then the novel catalyst is obtained through water removal, drying and roasting treatment;
wherein the aqueous modifying component solution comprises an acid, a metal salt and water; the acid is phosphoric acid and/or boric acid, and the metal salt is selected from nitrate of one or more of magnesium, calcium, strontium, barium, zinc, copper, cobalt, cerium, lanthanum and zirconium, preferably one or more of calcium nitrate, barium nitrate and magnesium nitrate hexahydrate.
9. The production method according to claim 8, wherein the mass concentration of the aqueous solution of the modifying component is 1 to 20%;
the weight ratio of the ZSM-5 molecular sieve to the SBA-16 all-silicon mesoporous molecular sieve to the modified component aqueous solution is 1: (0.3-1.6): (3-30);
the conditions of the contact reaction include: the temperature is 10-100 ℃ and the time is 0.5-50h;
the roasting conditions include: the temperature is 400-700 ℃ and the time is 2-20h.
10. Use of a novel catalyst according to any one of claims 1-7 in a reaction for producing low carbon olefins by direct conversion of waste plastics.
11. The application of claim 10, wherein the application comprises: the plastic powder is contacted with the novel catalyst to react;
and/or, the contacting conditions include: the temperature is 420-580 ℃, the pressure is 0.01-1MPa, and the contact time is 0.5-12h;
and/or the weight ratio of the novel catalyst to the amount of the waste plastic powder is 1: (0.5-50).
CN202210314372.6A 2022-03-28 2022-03-28 Novel catalyst, preparation method thereof and application thereof in reaction for preparing low-carbon olefin by directly converting waste plastics Pending CN116851030A (en)

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