CN108786898A - The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane - Google Patents
The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane Download PDFInfo
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- CN108786898A CN108786898A CN201710313759.9A CN201710313759A CN108786898A CN 108786898 A CN108786898 A CN 108786898A CN 201710313759 A CN201710313759 A CN 201710313759A CN 108786898 A CN108786898 A CN 108786898A
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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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to catalyst field, a kind of loaded catalyst and preparation method thereof, application and a kind of method of preparing propylene by dehydrogenating propane of the loaded catalyst in preparing propylene by dehydrogenating propane reaction are disclosed.Wherein, the loaded catalyst includes platinum component, tin component and the sodium component of carrier and load on the carrier, and the carrier is rodlike macroporous/mesoporous material, and the specific surface area of the rodlike macroporous/mesoporous material is 270-400m2/ g, pore volume 0.9-1.4cm3/ g, aperture 7-17nm.The reaction of loaded catalyst catalysis preparing propylene by dehydrogenating propane using the present invention, conversion of propane is high, and Propylene Selectivity is high.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of loaded catalyst, a kind of system of loaded catalyst
Preparation Method, application of the loaded catalyst in preparing propylene by dehydrogenating propane reaction, a kind of preparing propylene by dehydrogenating propane
Method.
Background technology
Propylene is the base stock of petrochemical industry, mainly for the production of polypropylene, acrylonitrile, acetone, propylene oxide, propylene
Acid and octyl alconyl etc..The supply half of propylene comes from refinery's by-product, separately has about 45% to come from steam cracking, a small amount of other replacement skills
Art.In recent years, the demand of propylene increases year by year, and traditional production of propylene has been unable to meet demand of the chemical industry to propylene,
Therefore propylene enhancing becomes a big hot spot of research.Wherein, preparing propylene by dehydrogenating propane is a major technique of propylene volume increase.10
For many years, preparing propylene by dehydrogenating propane has become the important process process of industrialization production of propylene.The major catalytic of dehydrogenating propane
Agent has in chromium oxide/aluminum oxide catalyst and Uop Inc.'s Oleflex techniques in ABB Lummus companies Catofin techniques
Platinum tin/aluminium oxide catalyst.Requirement of the chromium-based catalysts to raw material impurity is relatively low, on the low side compared with noble metal；But this
Class catalyst is easy carbon distribution inactivation, will be regenerated every 15-30 minutes once, and since the chromium in catalyst is heavy metal,
Environmental pollution is serious；Platinum-tin catalyst activity is high, and selectivity is good, can reach reaction time several days, can bear more harsh
Process conditions, and to more environment-friendly, but since noble metal platinum is expensive, cause catalyst cost higher.Third
Alkane dehydrogenation producing propylene technique realizes that industrialized production alreadys exceed 20 years, also many to the research of dehydrogenation, but current
Catalyst still there is conversion of propane it is not high and be easy to inactivation the defects of, require further improvement and perfect.Therefore, it develops
The propane dehydrogenation catalyst of function admirable has realistic meaning.
In order to improve the reactivity worth of propane dehydrogenation catalyst, researcher has done many work.Such as：(1) it uses and divides
Son sieve class carrier substitutes traditional γ-Al2O3Carrier, effect preferably include MFI type micro porous molecular sieve (CN104307555A,
CN101066532A, CN101380587A, CN101513613A), mesoporous MCM-41 molecular sieves (CN102389831A) and mesoporous
SBA-15 molecular sieves (CN101972664A, CN101972664B) etc.；(2) use calsil to γ-Al2O3Carrier is repaiied
Decorations, and the various active metal components of step impregnation and metal promoter (CN104368364A)；(3) with aluminium oxide and magnesia
Composite oxides are as carrier, and the various active metal components of step impregnation and metal promoter (CN104888818A).It is above-mentioned
The improved method of various propane dehydrogenation catalysts all can cause catalyst preparation process more cumbersome, and manufacturing cost increases, and prepare
Cycle stretch-out, or even can use and arrive the reagent or raw material unfavorable to environmental resource.
Invention content
The purpose of the present invention is overcoming, existing dehydrogenation preparation process is complicated, active metal component dispersion is uneven
Defect, a kind of loaded catalyst and its preparation method and application is provided.Loaded catalyst catalysis third using the present invention
The reaction of alkane preparing propylene by dehydrogenating, conversion of propane is high, and Propylene Selectivity is high.
Specifically, in a first aspect, the present invention provides a kind of loaded catalyst, which includes carrier and is supported on
Platinum component, tin component on the carrier and sodium component, wherein the carrier is rodlike macroporous/mesoporous material, described rodlike big
The specific surface area of hole mesoporous material is 270-400m2/ g, pore volume 0.9-1.4cm3/ g, aperture 7-17nm.
Second aspect, the present invention provides the preparation method of above-mentioned supported catalyst, this method includes：By carrier with contain
The mixed aqueous solution of water-soluble platinum compound, water-soluble tin compound and inorganic sodium carries out co-impregnation, then removes aqueous solvent,
It dries and roasts.
The third aspect, the present invention provides the loaded catalysts that the above method is prepared.
Fourth aspect, the present invention provides application of the above-mentioned loaded catalyst in preparing propylene by dehydrogenating propane reaction.
5th aspect, the present invention provides a kind of method of preparing propylene by dehydrogenating propane, this method includes：In dehydrogenating propane
Under conditions of preparing propylene, propane is contacted with catalyst, wherein the catalyst is that the support type that aforementioned present invention provides is urged
Agent.
Loaded catalyst using the present invention and method have the following advantages：(1) present invention utilizes macropore, specific surface area
The mesoporous material carrier larger, pore volume is larger prepares catalyst, and above structure feature is conducive to metal component in carrier surface
Fine dispersion, and then can ensure the propane dehydrogenation catalyst function admirable prepared；(2) present invention is substituted using co-impregnation method
Conventional step impregnation method, preparation process is simple, and condition is easily controllable, good repetitiveness；(3) catalysis provided by the invention
Agent shows good catalytic performance when being reacted for preparing propylene by dehydrogenating propane.Conversion of propane is high, and Propylene Selectivity is high, urges
Agent stability is good.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the X-ray diffracting spectrum of the rodlike macroporous/mesoporous material SBA-15-1 in embodiment 1；
Fig. 2 is nitrogen adsorption-desorption curve figure of the rodlike macroporous/mesoporous material SBA-15-1 in embodiment 1；
Fig. 3 is the pore structure schematic diagram (TEM transmission electron microscopes) of the rodlike macroporous/mesoporous material SBA-15-1 in embodiment 1；
Fig. 4 is the microscopic appearance figure (SEM scanning electron microscope) of the rodlike macroporous/mesoporous material SBA-15-1 in embodiment 1.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of loaded catalyst, the catalyst include carrier and be supported on carrier platinum component,
Tin component and sodium component, wherein the carrier is rodlike macroporous/mesoporous material, the specific surface area of the rodlike macroporous/mesoporous material
For 270-400m2/ g, pore volume 0.9-1.4cm3/ g, aperture 7-17nm.
Under preferable case, the specific surface area of the rodlike macroporous/mesoporous material is 300-380m2/ g, pore volume 0.9-
1.2cm3/ g, aperture 9-14nm.
In the present invention, specific surface area, pore volume and the aperture of the rodlike macroporous/mesoporous material can be inhaled according to nitrogen
Attached method measures.
According to the present invention, in the loaded catalyst, the platinum component, the content of tin component, sodium component and carrier
It can be changed in wide range, for example, on the basis of the total weight of the catalyst, based on the element, the platinum component contains
Amount can be 0.2-0.5 weight %, and the content of the tin component can be 0.2-1.2 weight %, and the content of the sodium component can
Think 0.3-0.8 weight %, the content of the carrier can be 97.5-99.3 weight %.In order to make dehydrogenation have more
Good catalytic performance and the manufacturing cost for reducing the dehydrogenation, under preferable case, with the total weight of the catalyst
On the basis of, based on the element, the content of the platinum component is 0.2-0.4 weight %, and the content of the tin component is 0.3-1 weights
% is measured, the content of the sodium component is 0.4-0.7 weight %, and the content of the carrier is 97.9-99.1 weight %.
In the present invention, the carrier is prepared by method comprising the following steps：By template, positive silicic acid second
Ester and sour agent are mixed, and obtained mixture is carried out crystallization, filtering and removed template method.In the present invention, institute
There is no particular limitation for the sequence being mixed for stating in the preparation process of carrier, can be by template, ethyl orthosilicate and acid
Agent is carried out at the same time mixing, can also mix arbitrary two kinds, the third component is then added and is uniformly mixed.According to a kind of preferred
Template and sour agent, are first uniformly mixed by embodiment, and silicon source is then added and is uniformly mixed.
In the present invention, the dosage of the template, ethyl orthosilicate and sour agent can change in wide range, example
Such as, the molar ratio of the template, ethyl orthosilicate and sour agent can be 1:50-80:100-500, preferably 1:55-65：
200-400。
In the present invention, the template can be the various templates of this field routine.For example, the template can be with
For triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene.Wherein, the template can be commercially available (for example,
Aldrich, trade name P123, molecular formula EO can be purchased from20PO70EO20, molecular weight Mn is that 5800), can also lead to
Existing various methods are crossed to be prepared.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the template
The molal quantity of agent calculates to obtain according to the average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene.
In the present invention, the sour agent can be various acidic aqueous solutions commonly used in the art, for example, can be salt
At least one of acid, sulfuric acid, nitric acid and hydrobromic acid aqueous solution, preferably aqueous hydrochloric acid solution.
There is no particular limitation for the dosage of the acid agent, can be changed in wide range, it is preferable that above-mentioned mixing connects
Tactile pH value is 1-7.
There is no particular limitation to the above-mentioned condition being mixed by the present invention, can be the conventional selection of this field.For example,
The condition being mixed includes：Temperature can be 10-60 DEG C, preferably 25-60 DEG C；Time can be 10-72 hours, excellent
It is selected as 10-30 hours；PH value can be 1-7, preferably 3-6.In order to be more advantageous to the uniform mixing between each substance, according to this hair
A kind of bright preferred embodiment, described be mixed carry out under agitation.
In the present invention, there is no particular limitation for the condition of the crystallization, can be the conventional selection of this field.Such as institute
The condition for stating crystallization includes：Temperature can be 30-150 DEG C, preferably 90-150 DEG C；Time can be 10-72 hours, preferably
10-40 hours.According to a kind of preferred embodiment, the crystallization is implemented by hydrothermal crystallization method.
In the present invention, in order to remove the impurity in carrier, the preparation method of the carrier preferably further includes the filtering
Washing later and drying process.The washing and drying process can be the conventional selection of this field, can be used for example
Ionized water or distilled water are washed at room temperature, are dried in 80-110 DEG C of drying box.By washing and drying
To mesoporous material raw powder.
In the present invention, the template can realize removing by way of washing and/or calcining.Washing can be water
It washes and/or alcohol is washed, washing removed template method condition includes：Temperature can be 90-120 DEG C, and the time can be 10-40 hours.Root
According to a kind of preferred embodiment, mesoporous material raw powder ethyl alcohol and/or water are washed under reflux conditions can remove template
Agent.Calcining removed template method condition include：Temperature can be 450-600 DEG C, and the time can be 8-20h.According to a kind of preferred
Embodiment, mesoporous material raw powder is calcined in Muffle furnace.
In the present invention, the loaded catalyst can be prepared according to the various conventional use of methods in this field, as long as
It being capable of Supported Pt Nanoparticles component, tin component and sodium component on the carrier.
The present invention also provides a kind of preparation method of loaded catalyst, this method includes：By carrier with containing water-soluble
Property platinum compounds, water-soluble tin compound and inorganic sodium mixed aqueous solution carry out co-impregnation, then remove aqueous solvent, it is dry
And it roasts.
Wherein, the carrier hereinbefore has been described, and details are not described herein.To the water-soluble platinum chemical combination in the present invention
There is no particular limitation for the selection of water-soluble platinum compound described in object, the water-soluble tin compound and the inorganic sodium.Example
Such as, the water-soluble platinum compound is at least one of chloroplatinic acid, ammonium chloroplatinate and platinum nitrate, preferably chloroplatinic acid and/or
Ammonium chloroplatinate, more preferably chloroplatinic acid；The water-soluble tin compound is butter of tin；The inorganic sodium be sodium nitrate and/
Or sodium chloride.
In the present invention, the dosage of the water-soluble platinum compound, water-soluble tin compound and inorganic sodium can compared with
It is changed in a wide range of, for example, the dosage of the water-soluble platinum compound, water-soluble tin compound and inorganic sodium preparing
In obtained loaded catalyst, on the basis of the total weight of the catalyst, based on the element, the content of the platinum component is
The content of 0.2-0.5 weight %, the tin component are 0.2-1.2 weight %, and the content of the sodium component is 0.3-0.8 weights
% is measured, the content of the carrier is 97.5-99.3 weight %.Under preferable case, the water-soluble platinum compound, water-soluble tin
The dosage for closing object and inorganic sodium makes in the loaded catalyst being prepared, using the total weight of the catalyst as base
Standard, based on the element, the content of the platinum component is 0.2-0.4 weight %, and the content of the tin component is 0.3-1 weight %, institute
The content for stating sodium component is 0.4-0.7 weight %, and the content of the carrier is 97.9-99.1 weight %.
In the present invention, the content of the platinum component in the loaded catalyst, tin component and sodium component is according to raw material
Rate of charge be calculated.
In the present invention, there is no particular limitation for the condition of the co-impregnation, such as the condition of the co-impregnation includes：Temperature
Degree can be 15-60 DEG C, and the time can be 1-10 hours；Preferably, temperature is 25-40 DEG C, and the time is 2-8 hours.
In the present invention, to the embodiment for removing aqueous solvent, there is no particular limitation, can be that this field is conventional
Embodiment, such as Rotary Evaporators may be used.
In the present invention, to the condition of the drying, there is no particular limitation, can be condition conventional in the art.Example
Such as, the condition of the drying includes：Temperature can be 90-160 DEG C, preferably 100-130 DEG C；Time can be 1-20h, preferably
For 2-5h.
In the present invention, to the condition of the roasting, there is no particular limitation, can be condition conventional in the art.Example
Such as, the condition of the roasting includes：Temperature can be 500-700 DEG C, preferably 550-650 DEG C；Time can be 2-15h, excellent
It is selected as 3-10h.
The present invention also provides the carried metallocene catalysts prepared by the above method.The load prepared by the method
Type catalyst has larger specific surface area and pore volume, and the dispersion situation of metal component on this carrier is preferable so that
The catalyst shows excellent catalytic performance in catalytic dehydrogenating reaction.
The present invention also provides application of the above-mentioned loaded catalyst in preparing propylene by dehydrogenating propane reaction.
The present invention also provides a kind of method of preparing propylene by dehydrogenating propane, this method includes：Third is prepared in dehydrogenating propane
Under conditions of alkene, propane is contacted with catalyst, the catalyst is above-mentioned loaded catalyst provided by the invention.
In the present invention, preparing propylene by dehydrogenating propane is carried out using catalyst provided by the invention, this field can be used conventional
The condition used, under preferable case, this method further includes that diluent gas is added, and the diluent gas is usually hydrogen.Described third
Alkane is contacted with catalyst to be carried out in fixed-bed quartz reactor, and the condition of the preparing propylene by dehydrogenating propane includes：Third
The molar ratio of alkane and hydrogen can be 0.5-5：1, reaction temperature can be 500-650 DEG C, and pressure can be 0.05-0.15MPa,
The mass space velocity of propane can be 1-10h-1.The pressure of the present invention is gauge pressure.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, writes a Chinese character in simplified form
For P123, molecular formula EO20PO70EO20, the substance for being 9003-11-6 in the registration number of U.S. chemical abstract, number-average molecular weight
Mn is 5800.
Rotary Evaporators produce for IKA companies of Germany, model RV10digital；
Drying box produces for Shanghai Yiheng Scientific Instruments Co., Ltd, model DHG-9030A；
Muffle furnace produces for CARBOLITE companies, model C WF1100.
X-ray diffraction analysis is on the X-ray diffractometer of the model D8Advance purchased from German Bruker AXS companies
It carries out；The N of sample2Adsorption-desorption experiment is the ASAP2020-M+C type adsorption instruments produced in Micromeritics companies of the U.S.
Upper progress, the specific surface area and pore volume of sample, which calculate, uses BET methods.
Scanning electron microscope (SEM) analysis is enterprising in the scanning electron microscope of the model XL-30 purchased from FEI Co. of the U.S.
Row；
The pore structure of sample is observed using the 20 type high resolution transmission electron microscopies of Tecnai of FEI Co..What is prepared is de-
Raw material feeds intake to calculate and determine when the content of each component passes through preparation in hydrogen catalyst；
Conversion of propane and selectivity are analyzed by gas-chromatography, and computational methods are as follows：
Primary quantity × 100% of amount/propane of the propane of conversion of propane=reaction consumption；
The computational methods of Propylene Selectivity are as follows：
Total flow × 100% of amount/propane of the propane of Propylene Selectivity=generation propylene consumption；
The computational methods of productivity of propylene are as follows：
Theoretical yield × 100% of actual production/propylene of productivity of propylene=propylene.
Embodiment 1
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) preparation of carrier
By 4.0 grams of triblock copolymer polyethylene glycol oxides-polypropylene oxide-polyethylene glycol oxide (Aldrich, P123)
It is added in the 16.4ml hydrochloric acid of a concentration of 37 weight % and the solution (pH=4.4) of 128ml water, is stirred to polyoxy at 40 DEG C
Change ethylene-polypropylene oxide-polyethylene glycol oxide to be completely dissolved, the ethyl orthosilicate of 8.86g be added in above-mentioned solution later,
It after 40 DEG C are stirred 24 hours, then transfers the solution into the reaction kettle of polytetrafluoroethyllining lining, baking oven crystallization 24 is small at 150 DEG C
Mesoporous material raw powder is obtained after Shi Houjing filterings, distillation water washing, drying.
It is washed 24 hours under conditions of obtained mesoporous material raw powder is flowed back using ethyl alcohol at 100 DEG C, removed template method,
Obtain rodlike macroporous/mesoporous material SBA-15-1.
SBA-15-1 is characterized with X-ray diffraction, transmission electron microscope, scanning electron microscope and nitrogen adsorption instrument.
Fig. 1 is X-ray diffracting spectrum, and abscissa is 2 θ, and unit is °, and the low-angle spectral peak occurred by XRD spectra can be with
Find out, mesoporous material SBA-15-1 has the hexagonal hole road structure of sequential 2 D specific to mesoporous material SBA-15.
Fig. 2 is nitrogen adsorption-desorption curve figure (abscissa is relative pressure, unit p/p0), the curve and document report
The nitrogen adsorption desorption curve of the SBA-15 in road is similar, shows that the SBA-15-1 of synthesis is mesoporous material.The aperture of SBA-15-1
Curve distribution is uniform, and peak shape symmetry is preferable.The aperture of mesoporous material SBA-15-1 is 12nm, specific surface area 351m2/ g, hole
Volume is 1.00cm3/g。
Fig. 3 is pore structure schematic diagram, it can be seen from the figure that mesoporous material SBA-15-1 keeps mesoporous material SBA-15 institute
The hexagonal hole road structure of distinctive sequential 2 D.
Fig. 4 is the microscopic appearance figure of mesoporous material SBA-15-1.It can be seen from the figure that the shape of mesoporous material SBA-15-1
Looks are consistent with the result of document report.
(2) preparation of loaded catalyst
By the H of 0.080g2PtCl6·6H2O, the SnCl of 0.207g4·5H2The NaNO of O and 0.185g3Be dissolved in 100ml go from
In sub- water, mixes with the rodlike macroporous/mesoporous material SBA-15-1 of the above-mentioned 10g being prepared, continuously stir at ambient temperature
Reaction 5 hours.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.It is 120 that solid product, which is placed in temperature,
DEG C drying box in, dry 3 hours.Then product is placed in Muffle furnace, temperature is 600 DEG C and roasts 6 hours, obtains support type
Catalyst A1.
The proportion of each component of loaded catalyst A1 is：Platinum components of the 0.3 weight % in terms of platinum element, 0.7 weight %
Tin component in terms of tin element, sodium components of the 0.5 weight % in terms of sodium element, remaining is rodlike macroporous/mesoporous material SBA-15-
1。
(3) preparing propylene by dehydrogenating propane
The loaded catalyst A1 of 0.5g is fitted into fixed-bed quartz reactor, controlling reaction temperature is 610 DEG C, reaction
Pressure is 0.1MPa, propane：The molar ratio of hydrogen is 1:1, propane mass space velocity is 3.0h-1, reaction time 50h.Reaction knot
Fruit is shown in Table 1.
Embodiment 2
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) preparation of carrier
By 4.0 grams of triblock copolymer polyethylene glycol oxides-polypropylene oxide-polyethylene glycol oxide (Aldrich, P123)
It is added in the 13.6ml hydrochloric acid of a concentration of 37 weight % and the solution of 128ml water, stirring is poly- to polyethylene glycol oxide-at 40 DEG C
Propylene oxide-polyethylene glycol oxide is completely dissolved, and the ethyl orthosilicate of 9.32g is added in above-mentioned solution later, 25 DEG C of stirrings
After 30 hours, then transfer the solution into the reaction kettle of polytetrafluoroethyllining lining, at 150 DEG C baking oven crystallization after 24 hours by
Mesoporous material raw powder is obtained after filtering, distillation water washing, drying.
By obtained mesoporous material raw powder in 500 DEG C of high-temperature calcination 10h of Muffle furnace, removed template method obtains rodlike macropore
Mesoporous material SBA-15-2.
The specific surface area of rodlike macroporous/mesoporous material SBA-15-2 is 300m2/ g, pore volume 0.9cm3/ g, aperture are
10nm。
(2) preparation of loaded catalyst
By the H of 0.053g2PtCl6·6H2O, the SnCl of 0.09g4·5H2The NaCl of O and 0.127g is dissolved in 50ml deionizations
In water, mixed with the rodlike macroporous/mesoporous material SBA-15-2 of the 10g of the above-mentioned thermal activation being prepared, it is continuous under the conditions of 40 DEG C
It is stirred to react 2 hours.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.Solid product is placed in temperature
In 100 DEG C of drying boxes, to dry 5 hours.Then in Muffle furnace, temperature is 650 DEG C and roasts 3 hours, obtains support type and urges
Agent A2.
The proportion of loaded catalyst A2 each components is：Platinum components of the 0.2 weight % in terms of platinum element, 0.3 weight % with
The tin component of tin element meter, sodium components of the 0.4 weight % in terms of sodium element, remaining is rodlike macroporous/mesoporous material SBA-15-2.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is substituted using loaded catalyst A2
Loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Embodiment 3
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) preparation of carrier
By 4.0 grams of triblock copolymer polyethylene glycol oxides-polypropylene oxide-polyethylene glycol oxide (Aldrich, P123)
It is added in the 27.2ml hydrochloric acid of a concentration of 37 weight % and the solution (pH=3) of 200ml water, is stirred to polyoxygenated at 40 DEG C
Ethylene-polypropylene oxide-polyethylene glycol oxide is completely dissolved, and the ethyl orthosilicate of 7.89g is added in above-mentioned solution later, 40
After DEG C stirring 24 hours, then transfer the solution into the reaction kettle of polytetrafluoroethyllining lining, baking oven crystallization 24 hours at 150 DEG C
Afterwards mesoporous material raw powder is obtained after filtering, distilling water washing, drying.
It is washed 24 hours under conditions of obtained mesoporous material raw powder is flowed back using deionized water at 100 DEG C, removes mould
Plate agent obtains rodlike macroporous/mesoporous material SBA-15-3.
The specific surface area of rodlike macroporous/mesoporous material SBA-15-3 is 378m2/ g, pore volume 1.2cm3/ g, aperture are
14nm。
(2) preparation of loaded catalyst
By the H of 0.11g2PtCl6·6H2O, the SnCl of 0.296g4·5H2The NaNO of O and 0.259g3Be dissolved in 200ml go from
It in sub- water, mixes, is continuously stirred under the conditions of 30 DEG C anti-with the rodlike macroporous/mesoporous material SBA-15-3 of the above-mentioned 10g being prepared
It answers 8 hours.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.It is 100 DEG C that solid product, which is placed in temperature,
Drying box in, dry 5 hours.Then in Muffle furnace, temperature is 550 DEG C and roasts 10 hours, obtains loaded catalyst A3.
The proportion of loaded catalyst A3 each components is：Platinum components of the 0.4 weight % in terms of platinum element, 1 weight % is with tin
The tin component of element meter, sodium components of the 0.7 weight % in terms of sodium element, remaining is rodlike macroporous/mesoporous material SBA-15-3.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is substituted using loaded catalyst A3
Loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Embodiment 4
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) preparation of carrier
Carrier is prepared according to the method for embodiment 1.
(2) preparation of loaded catalyst
It is carried out according to the method for embodiment 1, unlike, platinum component, tin component are different with the content of sodium component.Specifically
Ground, H2PtCl6·6H2The dosage of O is 0.133g, SnCl4·5H2The dosage of O is 0.355g, NaNO3Dosage be 0.111g,
It is remaining same as Example 1, obtain loaded catalyst A4.
The proportion of loaded catalyst A4 each components is：Platinum components of the 0.5 weight % in terms of platinum element, 1.2 weight % with
The tin component of tin element meter, sodium components of the 0.3 weight % in terms of sodium element, remaining is rodlike macroporous/mesoporous material SBA-15-1.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is substituted using loaded catalyst A4
Loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Comparative example 1
The method that this comparative example is used to illustrate the loaded catalyst and preparing propylene by dehydrogenating propane of reference
By the H of 0.080g2PtCl6·6H2O, the SnCl of 0.207g4·5H2The NaNO of O and 0.185g3Be dissolved in 100ml go from
In sub- water, the commercially γ-Al of 10g are added2O3(the Qingdao wave silica-gel desiccant company trade mark is technical grade low specific surface area to carrier
The commercially available product of activated alumina, specific surface area 162m2/ g, pore volume 0.82cm3/ g) mixing, it continuously stirs at ambient temperature
Mix reaction 5 hours.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.Solid product, which is placed in temperature, is
It is 3 hours dry in 120 DEG C of drying box.Then in Muffle furnace, temperature is 600 DEG C and roasts 6 hours, obtains supported catalyst
Agent DA1.
The proportion of each component of loaded catalyst DA1 is：Platinum components of the 0.3 weight % in terms of platinum element, 0.7 weight %
Tin component in terms of tin element, sodium components of the 0.5 weight % in terms of sodium element, remaining is γ-Al2O3Carrier.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is replaced using loaded catalyst DA1
For the loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Comparative example 2
The method that this comparative example is used to illustrate the loaded catalyst and preparing propylene by dehydrogenating propane of reference
Carrier and loaded catalyst are prepared according to the method for embodiment 1, unlike, the method for not using co-impregnation,
But the method for using step impregnation prepares loaded catalyst.Specifically, rodlike macroporous/mesoporous material SBA-15-1 is first existed
5h is impregnated in chloroplatinic acid aqueous solution, by the rodlike macroporous/mesoporous material SBA-15-1 of carrier after dipping according to the condition of embodiment 1
After being dried and roasting, then 5h is impregnated in the aqueous solution of butter of tin and sodium nitrate, then according to the condition of embodiment 1 into
Row is dry and roasts, and obtains loaded catalyst DA2.
The proportion of each component of loaded catalyst DA2 is：Platinum components of the 0.3 weight % in terms of platinum element, 0.7 weight %
Tin component in terms of tin element, sodium components of the 0.5 weight % in terms of sodium element, remaining is rodlike macroporous/mesoporous material SBA-15-
1。
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is replaced using loaded catalyst DA2
For the loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Table 1
From the results shown in Table 1, embodiment 1-4 loaded catalysts using the present invention are prepared for dehydrogenating propane
When the reaction of propylene, catalytic performance is substantially better than commercially available γ-Al2O3Catalyst (comparative example 1) prepared by carrier, propane
Average conversion, propylene average selectivity and propylene average yield are all significantly improved.Illustrate catalysis dehydrogenation provided by the invention
Agent preparation method may be implemented to improve the effect of dehydrogenation catalytic performance.Step impregnation legal system is used relative to comparative example 2
The preparation process of standby catalyst, catalyst of the present invention is simple, excellent catalytic effect.And use the embodiment 1- in preferred scope
3 it is with obvious effects optimal.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (11)
1. a kind of loaded catalyst, which includes platinum component, tin component and the sodium of carrier and load on the carrier
Component, which is characterized in that the carrier is rodlike macroporous/mesoporous material, and the specific surface area of the rodlike macroporous/mesoporous material is
270-400m2/ g, pore volume 0.9-1.4cm3/ g, aperture 7-17nm.
2. load raw catelyst according to claim 1, wherein the specific surface area of the rodlike macroporous/mesoporous material is
300-380m2/ g, pore volume 0.9-1.2cm3/ g, aperture 9-14nm.
3. loaded catalyst according to claim 1, wherein on the basis of the total weight of the catalyst, with element
The content of meter, the platinum component is 0.2-0.5 weight %, and the content of the tin component is 0.2-1.2 weight %, the sodium component
Content be 0.3-0.8 weight %, the content of the carrier is 97.5-99.3 weight %.
4. loaded catalyst according to claim 1, wherein the carrier is prepared by method comprising the following steps
It obtains：Template, ethyl orthosilicate and sour agent are mixed, and obtained mixture is subjected to crystallization, filtering simultaneously
Removed template method；
Preferably, the molar ratio of the template, ethyl orthosilicate and sour agent is 1:50-80:100-500；
Preferably, the template be triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, it is described acid agent be hydrochloric acid,
At least one of sulfuric acid, nitric acid and hydrobromic acid aqueous solution；
Preferably, the condition being mixed includes：Temperature is 10-60 DEG C, and the time is 10-72 hours, pH value 1-7；Institute
The condition for stating crystallization includes：Temperature is 30-150 DEG C, and the time is 10-72 hours；
Preferably, the condition of the removed template method includes：Temperature is 90-120 DEG C, and the time is 10-40 hours.
5. a kind of method preparing the loaded catalyst described in any one of claim 1-4, which is characterized in that this method
Including：Carrier and the mixed aqueous solution containing water-soluble platinum compound, water-soluble tin compound and inorganic sodium are subjected to total immersion
Stain, then removes aqueous solvent, and drying simultaneously roasts.
6. according to the method described in claim 5, wherein, the water-soluble platinum compound, water-soluble tin compound and inorganic sodium
The dosage of salt makes in the loaded catalyst being prepared, on the basis of the total weight of the catalyst, based on the element, institute
The content for stating platinum component is 0.2-0.5 weight %, and the content of the tin component is 0.2-1.2 weight %, and the sodium component contains
Amount is 0.3-0.8 weight %, and the content of the carrier is 97.5-99.3 weight %.
7. according to the method described in claim 5, wherein, the condition of the co-impregnation includes：Temperature is 15-60 DEG C, and the time is
1-10 hours；
Preferably, the condition of the roasting includes：Temperature is 500-700 DEG C, and the time is 2-15 hours.
8. the loaded catalyst prepared by the method described in any one of claim 5-7.
9. loaded catalyst the answering in preparing propylene by dehydrogenating propane reaction described in any one of claim 1-4 and 8
With.
10. a kind of method of preparing propylene by dehydrogenating propane, which is characterized in that this method includes：In preparing propylene by dehydrogenating propane
Under the conditions of, propane is contacted with catalyst, which is characterized in that the catalyst is described in any one of claim 1-4 and 8
Loaded catalyst.
11. according to the method described in claim 10, wherein, this method further includes that diluent gas hydrogen is added；
Preferably, the propane is contacted with catalyst carries out in fixed-bed quartz reactor, the preparing propylene by dehydrogenating propane
Condition include：The molar ratio of propane and hydrogen is 0.5-5：1, reaction temperature is 500-650 DEG C, pressure 0.05-
The mass space velocity of 0.15MPa, propane are 1-10h-1。
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| CN112138705A (en) * | 2019-06-28 | 2020-12-29 | 中国石油化工股份有限公司 | High-temperature and ball-milling modified SBA-15 molecular sieve material and preparation method thereof, propane dehydrogenation catalyst and preparation method and application thereof |
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