CN111135855B - Integral HZSM-5 molecular sieve catalyst for vegetable oil gas phase catalytic cracking and preparation method and application thereof - Google Patents

Integral HZSM-5 molecular sieve catalyst for vegetable oil gas phase catalytic cracking and preparation method and application thereof Download PDF

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CN111135855B
CN111135855B CN202010195237.5A CN202010195237A CN111135855B CN 111135855 B CN111135855 B CN 111135855B CN 202010195237 A CN202010195237 A CN 202010195237A CN 111135855 B CN111135855 B CN 111135855B
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molecular sieve
fiber
hzsm
catalyst
catalytic cracking
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CN111135855A (en
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李亚坤
张巧飞
朱春山
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Henan University of Technology
Zhengzhou University of Light Industry
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Henan University of Technology
Zhengzhou University of Light Industry
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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
    • 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
    • B01J29/42—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 containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a self-contained HZSM-5 molecular sieve catalyst for vegetable oil gas-phase catalytic cracking and a preparation method and application thereof, wherein the catalyst consists of a metal fiber matrix and a HZSM-5 molecular sieve layer uniformly coated on the outer surface of each fiber forming the matrix to form a coaxial sleeve type core-shell structure. The catalyst is prepared by pre-coating a seed crystal sol and then carrying out hydrothermal crystallization growth, has a three-dimensional open continuous network structure, and has a porosity of 65 to 85 percent. The catalyst has the advantages of stable structure, high permeability, good thermal conductivity and the like, can be applied to vegetable oil gas-phase catalytic cracking reaction, and has excellent catalytic activity and selectivity, the selectivity of gasoline products can reach 22% and the selectivity of diesel products can reach 58% when the total liquid product yield is 95%; in addition, the preparation method is simple, has a controllable structure, is suitable for industrial production, and has practical value and application prospect.

Description

Integral HZSM-5 molecular sieve catalyst for vegetable oil gas phase catalytic cracking and preparation method and application thereof
Technical Field
The invention relates to a self-contained HZSM-5 molecular sieve catalyst for vegetable fat gas-phase catalytic cracking, a preparation method and application thereof, in particular to a metal fiber structured HZSM-5 molecular sieve catalyst with a three-dimensional open continuous network structure, which consists of a self-contained sintered metal fiber matrix and an HZSM-5 molecular sieve layer growing on the matrix, a preparation method thereof and application thereof in vegetable fat gas-phase catalytic cracking reaction, belonging to the technical field of high-value utilization of molecular sieve materials and biomass energy.
Background
Fossil energy such as petroleum, coal, natural gas and the like constructs a foundation stone of the modern society and drives the continuous progress of the society. The domestic petroleum resources are relatively in shortage, the contradiction between supply and demand is very prominent, the dependence on external petroleum reaches more than 60 percent, and the method poses great threat to the safety of national energy strategy. In order to reduce the dependence on petroleum, the development of alternative fuels has been in the forefront. Biomass energy is a renewable energy source that converts solar energy into other forms of storage,the storage capacity of the fertilizer on the earth is large, the distribution and the sources are wide, and the fertilizer is not influenced by various environmental factors of geography and natural conditions. The biomass has the same components as conventional fossil fuel such as petroleum and coal, and has C, H, O as main component elements, and SO discharged during use 2 、NO x The gas content is relatively less, and the environmental pollution and the generation of acid rain can be effectively reduced. Therefore, in order to meet the challenges of the contradiction between international energy supply and demand, global climate change and the like, more and more countries develop biomass energy as an important strategic measure for replacing fossil energy and guaranteeing energy safety, the development and utilization of the biomass energy are actively promoted, and the role of the biomass energy in energy supply of many countries is continuously enhanced. As an energy source, china is in more shortage and should develop the innovative industry vigorously. Therefore, biomass energy is bound to become the primary choice for advocating energy conservation and emission reduction, promoting low-carbon economy and developing alternative energy in China.
The biodiesel or liquid hydrocarbon fuel prepared by utilizing the biomass such as vegetable oil, waste cooking oil and the like has the properties similar to petroleum fuel products, and is renewable clean energy with stable source. Currently, there are many ways to convert fats and oils into renewable liquid fuels, including physical and chemical methods. Physical methods include direct use, mixing and microemulsification; the chemical methods include esterification, ester exchange, thermal cracking and catalytic cracking. Compared with other methods, the ester exchange method utilizes the ester exchange reaction of grease and alcohol under the action of a catalyst to generate corresponding fatty acid ester, and is the main method for producing biodiesel at present (Fuel, 2008, 87, 3490-3496). The one-step or two-step base catalysis-transesterification reaction can obtain higher yield under proper reaction temperature and methanol/oil ratio (Fuel, 2008, 87, 2355-2373). The preparation of the biodiesel by using the environment-friendly solid catalyst and the heterogeneous catalysis-ester exchange method requires higher reaction temperature. The enzyme catalysis-ester exchange reaction has considerable yield under mild operation conditions, but the lipase is easy to be poisoned and inactivated and is expensive. It is worth to be noted that the ester exchange method has complex process, alcohol must be excessive in the production process, a corresponding alcohol recovery device is required in the subsequent process, a series of defects of high energy consumption, large equipment investment, difficult separation of byproduct glycerol and esterification products and the like exist, and the industrial continuous production is difficult to realize.
The catalytic cracking process for preparing liquid hydrocarbon fuel is a technological process for decomposing oil macromolecules into micromolecules and simultaneously converting low hydrogen-carbon ratio into higher hydrogen-carbon ratio. The hydrocarbon fuel prepared by the catalytic cracking method has the cetane number of 84-99 and the sulfur content of 0, and is high-quality ultra-clean fuel. Compared with the traditional ester exchange method, the device for preparing the hydrocarbon fuel by the catalytic cracking method is simple, the raw material source is wide, the adaptability is strong, the operation is flexible, the production cost is low, the industrialized production is easy to realize, and various clean fuels such as biogas, biogasoline, biodiesel and heavy bio-fuel oil (boiler fuel) can be obtained simultaneously (Bioresource technol, 2009, 100, 3036-3042). More importantly, the compositions of the products obtained by the two methods are different essentially, and the main component of the biodiesel prepared by the ester exchange method is fatty acid methyl ester; the liquid products produced by the catalytic cracking method are mainly a mixture of micromolecular alkane, olefin, carbonyl compounds, fatty acid and the like, the physicochemical properties of the liquid products are similar to those of common diesel oil, the liquid products have good low-temperature fluidity and low oxygen content, the heat value of the liquid products is close to that of the common diesel oil, and the liquid products have good fuel performance and higher cetane number (Energy conversion, management, 2014, 87, 378-384). The Yorkjing and the like use three kinds of grease of soybean oil, rubber seed oil and illegal cooking oil as raw materials to research on microporous molecular sieve USY and alkaline mesoporous molecular sieve K 2 The catalytic performance of the O-BaO-MCM-41 catalyst shows that after the soybean oil and rubber seed oil catalysts are repeatedly recycled for 6 times and the illegal cooking oil catalyst is repeatedly recycled for 4 times, the conversion rate and the liquid product yield are not obviously changed, and USY and K are proved 2 The O-BaO-MCM-41 has better repeated recycling performance (Naokjing, the research of catalytic cracking reaction of biological oil and fat, master academic paper, qingdao university of science and technology, 2013). Xu Junming and the like take different types of woody grease as raw materials, examine the performance of preparing biomass fuel by catalytic cracking on different catalysts, find that base catalysts can change the cracking reaction process and adjust the distillation range distribution of products, and the obtained liquid products have good performanceLow temperature fluidity (Bioresource technol., 2010, 101, 5586-5591). The Maria C.R. topic group utilizes different organosilanes to prepare beta nano molecular sieves with different structures and acidity, and further regulates the cracking selectivity of soybean oil by regulating the grain size, the quantity of framework aluminum and the acidity, thereby finally improving the product distribution (J. Mol. Catal. A: chem., 2016, 422, 89-102).
It is not difficult to find from the above reports that the control of the properties and composition of the fuel oil can be achieved by controlling the type and characteristics of the cracking catalyst. Among them, the molecular sieve catalyst with the molecular shape-selective effect is strongly noticed by scientists, and the yield of the liquid fuel is further improved and reasonable product distribution is obtained by regulating and controlling the pore size and distribution, the pore structure and the acidity. Currently, research efforts have focused on the modification of various molecular sieves (e.g., HZSM-5, MCM-41, USY, etc.), although some basic research results have shown very good C 5 -C 18 The selectivity improvement effect, but the practical application of the catalyst in the fixed bed reactor still faces huge challenges, mainly manifested by mass transfer/heat transfer limitations, high pressure drop, irregular flow, adverse effects of the use of the binder and the like on the selectivity and activity of the catalyst.
Currently, research in the field of heterogeneous catalysis in Microstructured Catalysts and Reactors (MCRs) is receiving increasing attention. Although the catalytic reaction is a surface/interface process, it is often limited at the macro-scale of the reactor by flow and transport constraints within the catalyst bed, resulting in a negative impact on catalyst activity and selectivity and even catalyst stability. The MCRs technique has been widely demonstrated to significantly optimize the hydrodynamic behavior of the solid catalyst bed and to enhance the mass/heat transfer properties within the catalyst bed. The MCRs technology has the advantage of allowing for precise design and control of catalyst size and shape details, up to the catalyst environment, with high flexibility in terms of controlling diffusion distance and porosity. The technology can decouple the factors (such as reaction dynamics, hydrodynamics and mass and heat transfer) coupled with each other in the traditional reactor, so that each factor can be independently optimized or regulated to a certain extent, and further the efficiency, selectivity and stability of the reaction process are improved. The SCRs technology considers a catalyst and a reactor as a whole, designs the catalyst from a macroscopic scale, and has the characteristic of becoming a powerful tool for innovation and process strengthening of industries such as petrochemical industry, energy chemical industry and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a self-contained HZSM-5 molecular sieve core-shell structure catalyst with excellent performance, high permeability and good thermal conductivity, a preparation method and application thereof, so that the optimized fluid flow and uniform residence time distribution in the vegetable oil catalytic cracking reaction are realized, the liquid hydrocarbon selectivity is further remarkably improved, and meanwhile, the rapid heat transfer is realized to eliminate local hot spots.
In order to solve the technical problem, the invention adopts the following technical scheme:
the invention relates to a monolithic HZSM-5 molecular sieve core-shell structure catalyst for vegetable oil gas phase catalytic cracking, which consists of a monolithic sintered metal fiber matrix and HZSM-5 molecular sieve layers uniformly coated on the outer surface of each metal fiber forming the matrix, and forms a three-dimensional open continuous network structure formed by a plurality of concentric cylindrical sleeves.
Preferably, the metal fiber matrix is copper fiber, nickel fiber, aluminum fiber, stainless steel fiber or titanium fiber.
More preferably, the diameter of each metal fiber is 2 to 50 micrometers.
As a preferred scheme, the HZSM-5 molecular sieve is SiO 2 /Al 2 O 3 The mole ratio of the silicon-aluminum molecular sieve is more than or equal to 50.
Preferably, the HZSM-5 molecular sieve accounts for 5 to 50 percent of the mass of the whole catalyst.
The preparation method of the metal fiber/HZSM-5 molecular sieve core-shell structure catalyst comprises the following steps:
a) Taking the integrally-packaged sintered metal fiber as a matrix, firstly carrying out surface pretreatment on the integrally-packaged sintered metal fiber, and then immersing the integrally-packaged sintered metal fiber into a suspension water solution consisting of silica sol and MFI type molecular sieve crystal seeds to prepare the integrally-packaged sintered metal fiber matrix precoated with the MFI type molecular sieve crystal seeds;
b) Putting the integrally-assembled sintered metal fiber matrix pre-coated with MFI type molecular sieve seed crystals into a molecular sieve crystallization liquid for hydrothermal crystallization growth;
c) Subjecting the obtained integral Na-type molecular sieve to NH treatment 4 And carrying out ion exchange on the Cl solution.
The operation of surface pretreatment of the integrally sintered metal fiber matrix is recommended as follows: putting the whole-package sintered metal fiber matrix into acetone, carrying out ultrasonic treatment for 0.5 to 1 hour, and then putting the mixture into a furnace for 80 to 120 hours o And C, drying in an oven.
As a preferable scheme, in the suspended aqueous solution obtained in the step a), the MFI type molecular sieve seed crystal accounts for 0.1-2% by mass, and the SiO is 2 The mass percentage of the composite material is 1% -5%.
As a further preferred scheme, the MFI type molecular sieve seed crystal is an MFI type all-silicon molecular sieve or SiO 2 /Al 2 O 3 The molar ratio of the silicon-aluminum molecular sieve is more than or equal to 50.
As a preferable scheme, the molecular sieve crystallization liquid in step b) is prepared from tetraethyl orthosilicate (TEOS) and sodium metaaluminate (NaAlO) 2 ) Tetrapropylammonium hydroxide (TPAOH) and deionized water in the following molar ratio, siO 2 : Al 2 O 3 : TPAOH:H 2 O =1 (0 to 0.01) and (0.1 to 0.5) are prepared.
As a preferable scheme, the conditions for carrying out hydrothermal crystallization growth are as follows: static crystallization is carried out for 24 to 72 hours at the temperature of 150 to 190 ℃.
As a preferred embodiment, the ion exchange conditions in step c) are as follows: ion exchange is carried out for 1 to 5 hours at the temperature of 60 to 90 ℃, and the mixture is washed, dried and roasted at 550 ℃ for 5 h.
The invention relates to an application of a catalyst with a core-shell structure of a self-contained HZSM-5 molecular sieve, which is used as a catalyst in a vegetable oil gas phase catalytic cracking process.
As a preferable scheme, the method for the vegetable oil gas phase catalytic cracking process comprises the following steps:
a) The integral HZSM-5 catalyst is filled in a cracking tube of the tubular reaction furnace, and nitrogen is introduced to empty the air in the reaction tube; the mass of the catalyst is 1-20% of the oil feeding amount.
b) Heating the cracking tube by using a two-section tube type heating furnace, wherein the temperature of a first section is set to be 360-400 ℃, and the grease is ensured to be fully preheated and gasified; the second-stage temperature is set according to the specific reaction temperature and ranges from 380 ℃ to 500 ℃.
c) Vegetable oil enters a cracking tube at a certain flow rate through a peristaltic pump, and is subjected to preheating and vaporization to generate continuous catalytic cracking reaction; the mass airspeed of the grease is 1 to 15 h -1 . Gaseous and liquid products are collected by a gas collection device and a liquid collection device, respectively.
d) Distilling the liquid product at normal pressure, collecting the distillate 205 at normal pressure o A gasoline fraction below C; then vacuum distilling, collecting 250 deg.C under reduced pressure o C or less.
Preferably, the vegetable oil and fat includes one of inedible vegetable oil such as castor oil, palm oil, cottonseed oil, and acidified oil or illegal cooking oil.
The invention has the beneficial effects that: the metal fiber/HZSM-5 molecular sieve core-shell structure catalyst provided by the invention has a three-dimensional open continuous network structure, the void ratio can reach 65-85%, and the metal fiber/HZSM-5 molecular sieve core-shell structure catalyst is high in permeability, good in heat conductivity and stable in structure; when the catalyst is used in the vegetable oil gas phase catalytic cracking reaction, the oil can be completely cracked, the yield of gasoline products reaches 22 percent, the yield of diesel oil products reaches 58 percent, and the generation of carbon deposition can be greatly inhibited; not only has simple structure and low operating cost, but also avoids the catalyst separation problem existing in the ester exchange method; therefore, compared with the prior art, the integral metal fiber/HZSM-5 molecular sieve core-shell structure catalyst provided by the invention has the advantages of remarkable progress and excellent catalytic effect, and the preparation method is simple, has a controllable structure, is suitable for industrial production, and has practical value and application prospect.
Drawings
FIG. 1 is a scanning electron micrograph of a monolithic SS-fiber/HZSM-5 core-shell structured catalyst prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of the monolithic Al-fiber/HZSM-5 core-shell structured catalyst prepared in example 2;
FIG. 3 is a scanning electron micrograph of a monolithic Al-fiber/HZSM-5 core-shell catalyst prepared in example 2;
FIG. 4 is a graph showing the effect of temperature on catalytic performance of the SS-fiber/HZSM-5 catalyst prepared in example 1 in a catalytic cracking reaction of castor oil;
FIG. 5 is a graph showing the effect of Si/Al ratio on catalytic performance in a catalytic cracking reaction of castor oil for Al-fiber/HZSM-5 catalyst prepared in example 2;
FIG. 6 is a GC-MS diagram of a gasoline fraction;
FIG. 7 is a GC-MS diagram of a diesel fraction;
FIG. 8 is a graph showing the effect of temperature on catalytic performance of the Ni-fiber/HZSM-5 catalyst prepared in example 3 in a palm oil catalytic cracking reaction.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are further described below:
example 1
1. Weighing 10 g of 30wt% silica sol, adding into a beaker filled with 290 g of distilled water, and uniformly mixing; then 0.6 g of MFI-type silicoaluminophosphate molecular Sieve (SiO) was added 2 : Al 2 O 3 = 200) seed crystal, and evenly mixing to obtain the seed crystal containing MFI type molecular sieve 0.2wt% and SiO 2 1wt% of a suspension;
2. weighing 2 g of stainless steel fiber sheet (fiber diameter is 20 micrometers, SS-fiber is abbreviated as follows) as a matrix, firstly putting the matrix into acetone for ultrasonic treatment for 0.5 hour, and then putting the matrix into a drying oven at 100 ℃ for drying; then the mixture is immersed in 0.2wt% of the prepared seed crystal containing the MFI type molecular sieve and SiO 2 1wt% of the suspension, holding for 10 minutes, taking out, drying in an oven at 100 ℃ overnight, and roasting in a muffle furnace at 450 ℃ for 2 hoursObtaining the integral stainless steel fiber SS-fiber matrix precoated with MFI type molecular sieve seed crystals.
3. Putting the prepared integral stainless steel fiber SS-fiber substrate precoated with MFI type molecular sieve seed crystal into a hydrothermal crystallization reaction kettle with a polytetrafluoroethylene lining, and adding tetraethyl orthosilicate (TEOS) and sodium metaaluminate (NaAlO) 2 ) Tetrapropylammonium hydroxide (TPAOH) and deionized water in the following molar ratio, siO 2 : Al 2 O 3 : TPAOH: H 2 And (3) adding 90 ml of crystallization liquid prepared from O =1, 0.005: 0.25:250, sealing the kettle, placing the kettle in an oven for static crystallization at 180 ℃ for 48 hours, taking out, washing, drying, and roasting the 5h in an air atmosphere at 550 ℃.
4. Subjecting the integrally-loaded Na-type molecular sieve prepared in the previous step to NH treatment 4 Cl solution (1 mol L) -1 ) After ion exchange for 3h at 70 ℃, cleaning, drying and roasting at 550 ℃ for 5h to obtain the self-contained SS-fiber/HZSM-5 core-shell structure catalyst.
Macroscopic measurements revealed that: in the monolithic SS-fiber/HZSM-5 core-shell catalyst prepared in this example, the ZSM-5 molecular sieve layer accounts for 5% by volume, the stainless steel fiber matrix accounts for 25% by volume, and the porosity is 70%.
Weighing to obtain: the weight percentage of the ZSM-5 molecular sieve-containing layer in the integral SS-fiber/HZSM-5 core-shell structure catalyst is 15 percent, and the weight percentage of the stainless steel fiber-containing matrix is 85 percent.
FIG. 1 is a scanning electron micrograph of a monolithic SS-fiber/HZSM-5 core-shell catalyst, as seen in FIG. 1: the molecular sieve layer is uniformly wrapped on the outer surface of each metal fiber forming the matrix.
In this example, the composition of the crystallization liquid in step 3 can be changed by changing sodium metaaluminate (NaAlO) 2 ) The addition amount of the compound is adjusted to prepare HZSM-5 molecular sieve shell layers with different silica-alumina ratios, and the rest is the same as the embodiment.
Example 2
1. Weighing 10 g of 30wt% silica sol, adding into a beaker filled with 290 g of distilled water, and uniformly mixing; then 0.3 g of MFI type all-silicon molecular sieve seed crystal is addedMixing to obtain seed crystal containing MFI type molecular sieve 0.1wt% and SiO 2 1wt% of a suspension;
2. weighing 2 g of aluminum fiber sheet (fiber diameter 30 micron, abbreviated as Al-fiber) as matrix, putting into acetone for ultrasonic treatment for 0.5 hr, and then putting into 100 hr o C, drying in an oven; then the mixture is immersed in 0.1wt% of the prepared seed crystal containing the MFI type molecular sieve and SiO 2 In 1wt% suspension, taking out after 10 minutes of ultrasonic treatment, and taking out at 100 deg.C o And drying in an oven C overnight to obtain the self-assembled aluminum fiber Al-fiber matrix precoated with MFI type molecular sieve seed crystals.
3. Putting the prepared integral aluminum fiber Al-fiber substrate precoated with MFI type molecular sieve crystal seeds into a hydrothermal crystallization reaction kettle with a polytetrafluoroethylene lining, and adding tetraethyl orthosilicate (TEOS) and sodium metaaluminate (NaAlO) 2 ) The molar composition prepared from tetrapropylammonium hydroxide (TPAOH) and deionized water is SiO 2 :Al 2 O 3 :TPAOH:H 2 O =1, 0.025 o C, statically crystallizing for 48 hours, taking out, washing, drying, and roasting 5h in 550 ℃ air atmosphere.
4. Subjecting the integrally-loaded Na-type molecular sieve prepared in the previous step to NH treatment 4 Cl solution (1 mol L) -1 ) After ion exchange for 5h at 90 ℃, washing, drying and roasting at 550 ℃ for 5h to obtain the self-contained Al-fiber/HZSM-5 core-shell structure catalyst.
FIG. 2 is the X-ray diffraction pattern of the obtained monolithic Al-fiber/HZSM-5 core-shell structure catalyst, and the XRD phase identification can confirm that the ZSM-5 molecular sieve composite material with the aluminum fiber structure is prepared.
Macroscopic measurements revealed that: in the monolithic Al-fiber/HZSM-5 catalyst with the core-shell structure prepared in the embodiment, the ZSM-5 molecular sieve layer accounts for 3% by volume, the aluminum fiber matrix accounts for 25% by volume, and the porosity is 72%.
Weighing to obtain: the weight percentage of the ZSM-5 molecular sieve layer in the self-contained Al-fiber/HZSM-5 core-shell structure catalyst is 12 percent, and the weight percentage of the stainless steel fiber matrix is 88 percent.
FIG. 3 is a scanning electron micrograph of a monolithic Al-fiber/HZSM-5 core-shell catalyst.
In this example, the composition of the crystallization liquid in step 3 can be changed by changing sodium metaaluminate (NaAlO) 2 ) The addition amount of the compound is adjusted to prepare HZSM-5 molecular sieve shell layers with different silica-alumina ratios, and the rest is the same as the embodiment.
Example 3
1. Weighing 30 g of 30wt% silica sol, adding into a beaker filled with 270 g of distilled water, and uniformly mixing; then 0.3 g of MFI type all-silicon molecular sieve seed crystal is added and mixed evenly to obtain 0.1wt% of seed crystal containing MFI type molecular sieve and SiO 2 3wt% of a suspension;
2. weighing 2 g of nickel fiber sheet (fiber diameter 5 micron, abbreviated as Ni-fiber) as matrix, putting into acetone, performing ultrasonic treatment for 0.5 hr, and then putting into 100 g o C, drying in an oven; then the mixture is immersed in 0.1wt% of the prepared seed crystal containing the MFI type molecular sieve and SiO 2 And (3) performing ultrasonic treatment on the suspension with the concentration of 3wt% for 15 minutes, taking out, and drying in an oven at 100 ℃ overnight to obtain the self-assembled nickel fiber Ni-fiber matrix with the MFI type molecular sieve seed crystal pre-coated.
3. Putting the prepared integral nickel fiber Ni-fiber substrate precoated with MFI type molecular sieve seed crystal into a hydrothermal crystallization reaction kettle with a polytetrafluoroethylene lining, and adding tetraethyl orthosilicate (TEOS) and sodium metaaluminate (NaAlO) 2 ) The molar composition prepared from tetrapropylammonium hydroxide (TPAOH) and deionized water is SiO 2 : Al 2 O 3 : TPAOH: H 2 In 90 ml of crystallization liquid prepared from O =1, 0.01: 300, statically crystallizing at 180 ℃ for 48 hours, taking out, washing, drying, and roasting at 550 ℃ in an air atmosphere of 5 h.
4. Subjecting the integrally-loaded Na-type molecular sieve prepared in the previous step to NH treatment 4 Cl solution (1 mol L) -1 ) After ion exchange for 5h at 80 ℃, washing, drying and roasting at 550 ℃ for 5h to obtain the self-contained Ni-fiber/HZSM-5 core-shell structure catalyst.
Weighing to obtain: the mass percent of the ZSM-5 molecular sieve-containing layer in the self-contained Ni-fiber/HZSM-5 core-shell structure catalyst is 20 percent, and the mass percent of the nickel-containing fiber matrix is 80 percent.
In this example, the composition of the crystallization liquid in step 3 can be changed by changing sodium metaaluminate (NaAlO) 2 ) The addition amount of the compound is adjusted to prepare HZSM-5 molecular sieve shell layers with different silica-alumina ratios, and the rest is the same as the embodiment.
Application example 1
The reaction performance of the self-contained SS-fiber/HZSM-5 core-shell structured catalyst prepared in example 1 in the catalytic cracking reaction of castor oil was examined on a fixed bed reactor. Filling SS-fiber/HZSM-5 catalyst into a cracking tube of a tubular reactor, and introducing nitrogen to exhaust the air in the reaction tube; heating the cracking tube by using a two-section tube type heating furnace, wherein the temperature of the first section is set to be 360 ℃, and the temperature of the second section is set according to the specific reaction temperature, and the range is 400-480 ℃. The castor oil enters a cracking pipe through a peristaltic pump for controlling the flow rate, continuous catalytic cracking reaction is carried out after preheating and vaporization, gaseous and liquid products are respectively collected through a gas collecting device and a liquid collecting device, and GC-MS analysis is carried out. Distilling the liquid product at normal pressure, and collecting gasoline fraction below 205 deg.C at normal pressure; then, the diesel oil fraction below 250 ℃ under reduced pressure is collected through reduced pressure distillation.
The yield of the liquid product is calculated as follows:
liquid product yield = mass of liquid product/mass of castor oil 100%
Reaction conditions are as follows: the catalyst has a Si/Al ratio of 150 and a mass space velocity of 6 h -1 Nitrogen flow 12.5 mLmin -1 . The effect of temperature on catalytic performance was examined under the above conditions and the results are shown in FIG. 4.
Application example 2
The reaction performance of the monolithic Al-fiber/HZSM-5 core-shell catalyst prepared in example 2 in the catalytic cracking reaction of castor oil was examined on a fixed bed reactor. Filling Al-fiber/HZSM-5 catalyst into a cracking tube of a tubular reaction furnace, and introducing nitrogen to empty the air in the reaction tube; heating the cracking tube by using a two-section tube type heating furnace, wherein the temperature of the first section is set to be 360 ℃, and the temperature of the second section is set according to the specific reaction temperature, and the range is 400-480 ℃. The castor oil enters a cracking tube by controlling the flow rate through a peristaltic pump, is preheated and vaporized to generate continuous catalytic cracking reaction, and gaseous and liquid products are respectively collected through a gas collecting device and a liquid collecting device and are subjected to GC-MS analysis. Distilling the liquid product at normal pressure, and collecting gasoline fraction below 205 deg.C at normal pressure; then, the diesel oil fraction below 250 ℃ under reduced pressure is collected through reduced pressure distillation.
The yield of the liquid product is calculated as follows:
liquid product yield = mass of liquid product/mass of castor oil 100%
Reaction conditions are as follows: the mass space velocity is 6 h -1 Nitrogen flow rate of 12.5 mLmin -1 The reaction temperature was 400 ℃. The influence of the ratio of silicon to aluminum on the catalytic performance was examined under the above conditions, and the experimental results are shown in fig. 5.
FIG. 6 is a GC-MS diagram of a gasoline fraction, which contains many substances having carbon atoms of C7 to C11 and boiling points of 60 to 160 ℃ and mainly contains heptane, octane, nonane, octene, nonene and other compounds.
FIG. 7 is a GC-MS chart of a diesel oil fraction, which shows a large number of peaks, a large number of C10-C18 substances, a boiling point range of 200-240 ℃ and 280-320 ℃, and mainly contains compounds such as undecanoic acid, undecane, heptadecene, octadecane and octadecanoic acid.
Application example 3
The reaction performance of the monolithic Ni-fiber/HZSM-5 core-shell structured catalyst prepared in example 3 in the catalytic cracking reaction of palm oil was examined on a fixed bed reactor. Filling Ni-fiber/HZSM-5 catalyst into the cracking tube of the tubular reaction furnace, and introducing nitrogen to exhaust the air in the reaction tube; heating the cracking tube by using a two-section tube type heating furnace, wherein the temperature of the first section is set to be 360 ℃, and the temperature of the second section is set according to the specific reaction temperature, and the range is 400-480 ℃. The palm oil is kept in a liquid state through a preheating device, the palm oil enters a cracking pipe through a peristaltic pump to generate continuous catalytic cracking reaction, and gaseous and liquid products are respectively collected through a gas collecting device and a liquid collecting device and are subjected to GC-MS analysis. Distilling the liquid product at normal pressure, and collecting gasoline fraction below 205 deg.C at normal pressure; then, the diesel oil fraction below 250 ℃ under reduced pressure is collected through reduced pressure distillation.
The yield of the liquid product is calculated as follows:
liquid product yield = mass of liquid product/mass of palm oil 100%
Reaction conditions are as follows: the catalyst has a silicon-aluminum ratio of 250 and a mass space velocity of 5h -1 Nitrogen flow rate of 10 mLmin -1 . The effect of temperature on catalytic performance was examined under the above conditions and the results are shown in FIG. 8.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (1)

1. The application of the integral Al-fiber/HZSM-5 core-shell structure catalyst in the catalytic cracking reaction of castor oil is characterized in that: filling Al-fiber/HZSM-5 catalyst into a cracking tube of a tubular reaction furnace, and introducing nitrogen to empty the air in the reaction tube; heating the cracking tube by using a two-section tube type heating furnace, wherein the temperature of the first section is set to be 360 ℃, and the temperature of the second section is set to be 400-480 ℃; the castor oil enters a cracking pipe at a flow speed controlled by a peristaltic pump, is preheated and vaporized to generate continuous catalytic cracking reaction, and gaseous and liquid products are respectively collected by a gas collecting device and a liquid collecting device and are subjected to GC-MS analysis; distilling the liquid product at normal pressure, and collecting gasoline fraction below 205 deg.C at normal pressure; then, carrying out reduced pressure distillation, and collecting diesel oil fraction below 250 ℃ under reduced pressure;
the preparation method of the self-contained Al-fiber/HZSM-5 core-shell structure catalyst comprises the following steps:
(1) Weighing 10 g of 30wt% silica sol, and adding into the containerMixing in 290 g distilled water beaker; then 0.3 g of MFI type all-silicon molecular sieve seed crystal is added and mixed evenly to obtain 0.1wt% of seed crystal containing MFI type molecular sieve and SiO 2 1wt% of a suspension;
(2) Weighing Al-fiber 2 g of an aluminum fiber sheet with the fiber diameter of 30 micrometers as a matrix, putting the matrix into acetone for ultrasonic treatment for 0.5 hour, and then putting the matrix into a reactor for 100 hours o C, drying in an oven; then the mixture is immersed in 0.1wt% of the prepared MFI-type molecular sieve-containing seed crystal and SiO-containing seed crystal 2 In 1wt% suspension, taking out after 10 minutes of ultrasonic treatment, and taking out at 100 deg.C o Drying in an oven for overnight to obtain a self-assembled aluminum fiber Al-fiber matrix precoated with MFI type molecular sieve seed crystals;
(3) Putting the prepared integral aluminum fiber Al-fiber substrate precoated with MFI type molecular sieve crystal seeds into a hydrothermal crystallization reaction kettle with a polytetrafluoroethylene lining, and adding tetraethyl orthosilicate (TEOS) and sodium metaaluminate (NaAlO) 2 ) The molar composition prepared from tetrapropylammonium hydroxide (TPAOH) and deionized water is SiO 2 : Al 2 O 3 : TPAOH: H 2 O =1, 0.025:0.25:250 in 90 ml of crystallization solution at 170 o C, performing static crystallization for 48 hours, taking out, washing, drying, and roasting the 5h in an air atmosphere at 550 ℃ to obtain the integral Na-type molecular sieve;
(4) Subjecting the obtained integral Na type molecular sieve to 1 mol L -1 NH 4 And carrying out ion exchange on the Cl solution at 90 ℃ for 5h, cleaning, drying and roasting the Cl solution at 550 ℃ for 5h to obtain the integral Al-fiber/HZSM-5 core-shell structure catalyst.
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