CN107262158B - The spherical mesoporous composite material of attapulgite containing aluminium and loaded catalyst and its preparation method and application and acid isopropyl preparation method - Google Patents
The spherical mesoporous composite material of attapulgite containing aluminium and loaded catalyst and its preparation method and application and acid isopropyl preparation method Download PDFInfo
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- CN107262158B CN107262158B CN201610213432.XA CN201610213432A CN107262158B CN 107262158 B CN107262158 B CN 107262158B CN 201610213432 A CN201610213432 A CN 201610213432A CN 107262158 B CN107262158 B CN 107262158B
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- B01J32/00—
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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
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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Abstract
The present invention relates to catalyst fields, and in particular to it is a kind of spherical shape the mesoporous composite material of attapulgite containing aluminium and loaded catalyst and its preparation method and application and acid isopropyl preparation method.Wherein, disclose a kind of spherical mesoporous composite material of attapulgite containing aluminium and preparation method thereof, the spherical shape mesoporous composite material of attapulgite containing aluminium prepared by this method, loaded catalyst containing the spherical shape mesoporous composite material of attapulgite containing aluminium, the preparation method of the loaded catalyst, the loaded catalyst prepared by this method, the application of the loaded catalyst in the esterification reaction.Wherein, the composite material contains attapulgite and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, and the content of aluminium element is 5-30 weight % in the composite material.The conversion ratio of reaction raw materials can be significantly improved in acid isopropyl preparation process as loaded catalyst made of carrier using composite material provided by the invention.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of spherical shape mesoporous composite material of attapulgite containing aluminium, the spherical shape
The preparation method of the mesoporous composite material of attapulgite containing aluminium, the composite mesoporous material of spherical shape attapulgite containing aluminium prepared by this method
Material, the loaded catalyst containing the spherical shape mesoporous composite material of attapulgite containing aluminium, the preparation method of the loaded catalyst,
The loaded catalyst prepared by this method, the application of the loaded catalyst in the esterification reaction, and use the support type
The method of catalyst preparation acid isopropyl.
Background technique
Acid isopropyl is transparent oily liquid, can be dissolved each other with animal and vegetable oil, and the coefficient of dispersion is big, and spreadability is good, can be
Thin electrolyte film is formed on skin, and there is skin care effect.With the rapid development of chemical industry, the demand to acid isopropyl is continuous
Increase.Under normal circumstances, acid isopropyl is made by esterification under the effect of the catalyst by oleic acid and isopropanol.It passes
System is liquid organic acid for oleic acid and the catalyst of isopropanol esterification, but because the pair that its corrosiveness is big, causes is anti-
Product separates the defects of complicated and liquid waste processing is difficult and its use is caused to be subject to certain restrictions after Ying Duo, reaction.With
Increase of the whole world to Catalytic processes greenization attention degree, solid acid catalysis technique replace liquid acid Catalytic processes gesture must
Row.
In existing loaded catalyst, meso-porous molecular sieve material is as carrier.Meso-porous molecular sieve material has duct
Orderly, the advantages that aperture is adjustable, specific surface area and hole appearance are larger, so that being made using these meso-porous molecular sieve materials as carrier
Loaded catalyst show lot of advantages in preparation process in organic catalytic reaction, for example, catalytic activity is high, secondary anti-
Should less, post-processing it is simple etc., however, big specific surface area and high hole hold so that these meso-porous molecular sieve materials have it is stronger
Water suction, moisture absorption ability, reunite in catalytic reaction process to will lead to these loaded catalysts, and then reduce oleic acid
The conversion ratio of oleic acid in isopropyl ester preparation process.Therefore, a kind of novel acid isopropyl that is used to prepare further is developed
Catalyst becomes problem in the urgent need to address.
Summary of the invention
The purpose of the invention is to overcome making using loaded catalyst made of existing meso-porous molecular sieve material
It is concave-convex containing aluminium to provide a kind of spherical shape for being suitable as carrier for the lower defect of reaction raw materials conversion ratio during standby acid isopropyl
Stick stone mesoporous composite material, the preparation method of the spherical shape mesoporous composite material of attapulgite containing aluminium, the spherical shape prepared by this method
The mesoporous composite material of attapulgite containing aluminium, the loaded catalyst containing the spherical shape mesoporous composite material of attapulgite containing aluminium should
The preparation method of loaded catalyst, the loaded catalyst prepared by this method, the loaded catalyst is in the esterification reaction
Application, and the method for preparing acid isopropyl using the loaded catalyst.
In order to achieve the above object, the present inventor is distributed by finding after research with one-dimensional channels diplopore
Attapulgite is introduced in the meso-porous molecular sieve material of structure, enters attapulgite in the duct of meso-porous molecular sieve material, and
The mesoporous composite material is made to the spherical shape for being not susceptible to reunite, the high-ratio surface of meso-porous molecular sieve material can be retained in this way
Product, macropore hold, large aperture and have the characteristics that one-dimensional channels diplopore distributed architecture, and can reduce the group of meso-porous molecular sieve material
It is poly-, increase its mobility；Simultaneously as aluminium element is introduced in meso-porous molecular sieve material, so that sphere intensity increases, as load
Body repeated multiple times can use.In addition, using loaded catalyst made of the mesoporous composite material to be used to prepare oleic acid different
The conversion ratio of reaction raw materials can be significantly improved when propyl ester.
For this purpose, the present invention provides a kind of spherical mesoporous composite materials of attapulgite containing aluminium, wherein the spherical shape is concave-convex containing aluminium
Stick stone mesoporous composite material contains attapulgite and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, and should
The average grain diameter of the spherical shape mesoporous composite material of attapulgite containing aluminium is 30-60 microns, and specific surface area is 100-600 meters squared per gram,
Pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal the first most probable pore size and second that respectively corresponds most may be used
Several apertures, first most probable pore size are 1-9 nanometers, and second most probable pore size is 39-45 nanometers；It is described spherical containing aluminium
The content of aluminium element is 5-30 weight %, preferably 10-25 weight % in attapulgite mesoporous composite material.
The present invention also provides a kind of method for preparing the spherical mesoporous composite material of attapulgite containing aluminium, this method include with
Lower step:
(1) providing meso-porous molecular sieve material or preparation with one-dimensional channels diplopore distributed architecture has one-dimensional channels double
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a, the component b and attapulgite are subjected to mixing and ball milling in high alumina ceramic ball grinder, and
Obtained slurry, is then spray-dried by the solid powder water slurrying that will be obtained after ball milling；
Wherein, above-mentioned steps make the average grain diameter of the spherical mesoporous composite material of attapulgite containing aluminium be that 30-60 is micro-
Rice, specific surface area are 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal point
Not Dui Ying the first most probable pore size and the second most probable pore size, first most probable pore size be 1-9 nanometers, described second most may be used
Several apertures are 39-45 nanometers；The content of aluminium element is 5-30 weight % in the spherical shape mesoporous composite material of attapulgite containing aluminium,
Preferably 10-25 weight %.
The present invention also provides the spherical shape mesoporous composite materials of attapulgite containing aluminium prepared by the above method.
The present invention also provides a kind of loaded catalyst, which contains pair of carrier and load on the carrier
Toluenesulfonic acid, wherein the carrier is the spherical mesoporous composite material of attapulgite containing aluminium according to the present invention.
The present invention also provides a kind of methods for preparing loaded catalyst, this method comprises: by carrier, p-methyl benzenesulfonic acid
It is uniformly mixed with water, and obtained mixture is spray-dried, wherein the carrier is the spherical shape according to the present invention
The mesoporous composite material of attapulgite containing aluminium.
The present invention also provides the loaded catalysts prepared by the above method.
The present invention also provides the application of above-mentioned loaded catalyst in the esterification reaction.
The present invention also provides a kind of preparation methods of acid isopropyl, this method comprises: in the presence of a catalyst,
Under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl, wherein the catalyst is the present invention
The loaded catalyst.
The spherical shape mesoporous composite material of attapulgite containing aluminium according to the present invention, combines with one-dimensional channels diplopore point
The advantages of meso-porous molecular sieve material of cloth structure, attapulgite, aluminium element and ball type carrier, so that the spherical shape concave convex rod containing aluminium
Stone mesoporous composite material is suitable as the carrier of loaded catalyst, is especially suitable as in acid isopropyl preparation process
The carrier of the loaded catalyst used.
In loaded catalyst of the present invention, the spherical shape mesoporous composite material of attapulgite containing aluminium as carrier has
There is the characteristics of porous structure of meso-porous molecular sieve material, and be also loaded p-methyl benzenesulfonic acid, so that the loaded catalyst was both
Have the advantages that loaded catalyst such as catalytic activity is high, side reaction is few, post-processing is simple etc., and there is the catalytic performance of acid,
So that the loaded catalyst not will lead to equipment corrosion not only when in acid isopropyl preparation process, but also can be with
Significantly improve the conversion ratio of reaction raw materials.
In addition, the loaded catalyst can be with when the method by spray drying prepares the loaded catalyst
It is used repeatedly, and still can obtain higher reaction raw materials conversion ratio during recycling.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffraction spectrogram of the spherical mesoporous composite material of attapulgite containing aluminium according to the present invention；
Fig. 2 is the SEM scanning of the microscopic appearance of the spherical mesoporous composite material of attapulgite containing aluminium according to the present invention
Electron microscope；
Fig. 3 is the graph of pore diameter distribution of the spherical mesoporous composite material of attapulgite containing aluminium according to the present invention.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of spherical mesoporous composite materials of attapulgite containing aluminium, wherein the spherical shape attapulgite containing aluminium
Mesoporous composite material contains attapulgite and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, and the spherical shape
The average grain diameter of the mesoporous composite material of attapulgite containing aluminium is 30-60 microns, and specific surface area is 100-600 meters squared per gram, hole body
Product is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal respectively corresponds the first most probable pore size and the second most probable hole
Diameter, first most probable pore size are 1-9 nanometers, and second most probable pore size is 39-45 nanometers；It is described spherical concave-convex containing aluminium
The content of aluminium element is 5-30 weight %, preferably 10-25 weight % in stick stone mesoporous composite material.
The spherical shape mesoporous composite material of attapulgite containing aluminium according to the present invention has one-dimensional channels diplopore distributed architecture,
The average grain diameter of its particle is measured using laser fineness gage, and specific surface area, pore volume and most probable pore size are inhaled according to nitrogen
Attached method measures.In the present invention, the average grain diameter is average grain diameter.
The spherical shape mesoporous composite material of attapulgite containing aluminium according to the present invention, by the way that spherical attapulgite containing aluminium is situated between
The particle size of hole composite material controls within above range, it can be ensured that the composite mesoporous material of the spherical shape attapulgite containing aluminium
Material is not susceptible to reunite, and is used as loaded catalyst made of carrier and can be improved in acid isopropyl preparation process
Reaction raw materials conversion ratio.When the specific surface area of the spherical mesoporous composite material of attapulgite containing aluminium is less than 100 meters squared per grams
And/or pore volume less than 0.5 ml/g when, the catalytic activity for being used as loaded catalyst made of carrier can significantly drop
It is low；When the specific surface area of the spherical mesoporous composite material of attapulgite containing aluminium is big greater than 600 meters squared per grams and/or pore volume
When 1.5 mls/g, it is used as the group of being easy to happen in acid isopropyl preparation process of loaded catalyst made of carrier
It is poly-, to influence the reaction raw materials conversion ratio in acid isopropyl preparation process.
In the preferred case, the average grain diameter of the spherical mesoporous composite material of attapulgite containing aluminium is 35-60 microns, than
Surface area is 100-600 meters squared per gram, and pore volume is 0.7-1.4 mls/g, and first most probable pore size is 2-9 nanometers,
Second most probable pore size is 39-42 nanometers.
In the present invention, the aluminium element can carry out ball milling by attapulgite and/or in high alumina ceramic ball grinder
Mode introduce.The attapulgite can be attapulgite commonly used in the art, under preferable case, the attapulgite
The content of middle aluminium element is 1-10 weight %, preferably 2-8 weight %.It is further preferred that the spherical shape attapulgite containing aluminium
The weight percent of aluminium element is greater than the weight percent of aluminium element in the attapulgite in mesoporous composite material.
According to the present invention, relative to the mesopore molecular sieve described in 100 parts by weight with one-dimensional channels diplopore distributed architecture
Material, the content of the attapulgite are 1-100 parts by weight, preferably 25-100 parts by weight, preferably 15-50 parts by weight.
In the present invention, the spherical mesoporous composite material of attapulgite containing aluminium can also contain two introduced by silica gel
Silica." silica introduced by silica gel " refers to the preparation in the spherical mesoporous composite material of attapulgite containing aluminium
Cheng Zhong, by silica gel as the silica for preparing raw material and bringing into the spherical mesoporous composite material of attapulgite containing aluminium finally prepared
Component.In the spherical mesoporous composite material of attapulgite containing aluminium, relative to double with one-dimensional channels described in 100 parts by weight
The meso-porous molecular sieve material of pore size distribution structure, the content of the silica introduced by silica gel can be 1-200 parts by weight,
Preferably 50-150 parts by weight, more preferably 75-150 parts by weight.
In the present invention, the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture can be normal for this field
The meso-porous molecular sieve material used is advised, and can be prepared according to the conventional method.
The present invention also provides a kind of method for preparing the spherical mesoporous composite material of attapulgite containing aluminium, this method include with
Lower step:
(1) providing meso-porous molecular sieve material or preparation with one-dimensional channels diplopore distributed architecture has one-dimensional channels double
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a, the component b and attapulgite are subjected to mixing and ball milling in high alumina ceramic ball grinder, and
Obtained slurry, is then spray-dried by the solid powder water slurrying that will be obtained after ball milling；
Wherein, above-mentioned steps make the average grain diameter of the spherical mesoporous composite material of attapulgite containing aluminium be that 30-60 is micro-
Rice, specific surface area are 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal point
Not Dui Ying the first most probable pore size and the second most probable pore size, first most probable pore size be 1-9 nanometers, described second most may be used
Several apertures are 39-45 nanometers；The content of aluminium element is 5-30 weight % in the spherical shape mesoporous composite material of attapulgite containing aluminium,
Preferably 10-25 weight %.
In the preferred case, the component a makes the average grain diameter of the spherical mesoporous composite material of attapulgite containing aluminium
It is 35-55 microns, specific surface area is 100-600 meters squared per gram, and pore volume is 0.8-1.2 mls/g, first most probable
Aperture is 1-9 nanometers, and second most probable pore size is 42-44 nanometers.
In step (1), the process with the filter cake of meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture is prepared
It may include: to be contacted tetramethoxy-silicane with sour agent, and will in the presence of template, trimethylpentane and ethyl alcohol
The mixture obtained after contact carries out crystallization and filtering.
The template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane molar ratio can be 1:100-500:200-
500:50-200, preferably 1:180-400:250-400:70-150.
The template can be various templates commonly used in the art.Preferably, the template is three block
Copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, the template can be commercially available (for example, can be purchased from
Aldrich, trade name P123, molecular formula EO20PO70EO20), it can also be prepared by existing various methods
It arrives.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxyethylene-
The average molecular weight of polyoxypropylene polyoxyethylene calculates to obtain.
The acid agent can be used for adjusting the substance or mixture (such as solution) of pH value for various routines.The acid agent
It is preferred that using in form of an aqueous solutions, pH value can be 1-6, preferably 3-5.It is highly preferred that it is 1-6 that the acid agent, which is pH value,
The acetic acid and sodium acetate buffer solution of (more preferable 3-5).
The condition that tetramethoxy-silicane is contacted with sour agent may include: that temperature is 10-60 DEG C, and the time is 10-72 hours, pH
Value is 1-7.In order to be more advantageous to the uniform mixing between each substance, the tetramethoxy-silicane is contacted preferably with sour agent in stirring bar
It is carried out under part.The dosage of the acid agent is preferably so that the pH value of tetramethoxy-silicane and the haptoreaction system of sour agent is 1-7.
The condition of the crystallization may include: that temperature is 30-150 DEG C, and the time is 10-72 hours.It is described under preferable case
The condition of crystallization includes: that temperature is 40-100 DEG C, and the time is 10-48 hours.The crystallization is implemented by hydrothermal crystallization method.
During above-mentioned preparation has the filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, pass through
Filtering with the process for obtaining filter cake may include: after filtration, wash that (washing times can be 2- repeatedly with deionized water
10) it, is then filtered.
In step (1), " providing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture " be can be directly
The product for weighing or choosing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture is also possible to preparation with one-dimensional
The meso-porous molecular sieve material of duct diplopore distributed architecture.The meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture
Preparation method can implement according to the conventional method, for example, preparation method may include: according to the above method preparation have
The filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture then by gained filtration cakes torrefaction, and will obtain after drying
Product in template removal.The condition of the removed template method may include: that temperature is 300-600 DEG C, time 10-80
Hour.
In step (2), the process for preparing the filter cake of silica gel may include: to carry out waterglass and inorganic acid and glycerine
Contact, and the mixture obtained after contact is filtered.
There is no particular limitation for the condition that waterglass is contacted with inorganic acid and glycerine, can be according to the routine for preparing silica gel
It is suitably determined in technique.Under preferable case, the condition that waterglass is contacted with inorganic acid and glycerine may include: that temperature is
10-60 DEG C, preferably 20-40 DEG C；Time is 1-5 hours, preferably 1.5-3 hours；PH value is 2-4.
In order to be more advantageous to the uniform mixing between each substance, waterglass and inorganic acid and the catalytic process of glycerine are excellent
Choosing carries out under agitation.
The waterglass is the aqueous solution of sodium metasilicate, and concentration can be 10-50 weight %, preferably 12-30 weight %.
The inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulfuric acid, nitric acid and hydrochloric acid
At least one of.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution.The nothing
The dosage of machine acid is preferably so that the pH value of the haptoreaction system of waterglass and inorganic acid is 2-4.
In step (2), " providing silica gel ", which can be, directly weighs or chooses silica gel product, is also possible to prepare silica gel.
The method for preparing silica gel can be implemented according to the conventional method, such as may include: the filter cake that silica gel is prepared according to the above method,
Then by gained filtration cakes torrefaction.
In step (3), relative to the component a of 100 parts by weight, the dosage of the component b is 1-200 parts by weight,
Preferably 75-150 parts by weight；The dosage of the attapulgite is 1-100 parts by weight, preferably 25-100 parts by weight.
In step (3), there is no particular limitation for concrete operation method and condition of the present invention to ball milling, not destroy or
Substantially carrier structure is not destroyed and enters silica gel subject in carrier duct.Those skilled in the art can select according to mentioned above principle
Various suitable conditions are selected to implement the present invention.In situations where it is preferred, the ball milling can carry out in the ball mill, the ball
The inner wall of ball grinder is high alumina ceramic in grinding machine, and the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can root
It is reasonably selected according to the size of ball grinder, 1 abrading-ball usually can be used in the ball grinder for being 50-150ml for size；
The material of the abrading-ball is high alumina ceramic.In situations where it is preferred, the content of aluminium element is 30-40 weight in the high alumina ceramic
Measure %.There is no particular limitation in source of the present invention to the high alumina ceramic ball grinder, for example, can be commercially available.Institute
It can be 300-500r/min that the condition for stating ball milling, which may include: the revolving speed of abrading-ball,；Temperature in high alumina ceramic ball grinder can be with
It is 15-100 DEG C, preferably 40-80 DEG C；The time of ball milling can be 0.1-100 hours, preferably 0.5-10 hours.
In step (3), by the process of the solid powder water slurrying obtained after ball milling can at 25-60 DEG C into
Row.In pulping process, the weight ratio of the dosage of solid powder and water can be 1:0.1-2, preferably 1:0.3-1, more preferably
For 1:0.5-1.
In step (3), the spray drying can be implemented according to conventional mode, for example, can in atomizer into
Row.The condition of the spray drying may include: that temperature is 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/
min；Under preferable case, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-
13000r/min。
In step (3), when the filter that the component a is the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture
Cake, when the component b is the filter cake of silica gel, namely when step (1) is that preparation has the mesoporous of one-dimensional channels diplopore distributed architecture
The process of the filter cake of molecular screen material, when step (2) is the process for the filter cake for preparing silica gel, the spherical shape attapulgite containing aluminium is situated between
The preparation method of hole composite material can also include: after the spray drying of step (3), from the product that spray drying obtains
Removed template method.The condition of the removed template method may include: that temperature is 300-600 DEG C, and the time is 10-80 hours；It is preferred that
In the case where, temperature is 450-550 DEG C, and the time is 15-70 hours.
The present invention also provides the spherical shape mesoporous composite materials of attapulgite containing aluminium prepared by the above method.
The present invention also provides a kind of loaded catalyst, which contains pair of carrier and load on the carrier
Toluenesulfonic acid, wherein the carrier is the above-mentioned spherical mesoporous composite material of attapulgite containing aluminium provided by the invention.
In the loaded catalyst, there is no particular limitation for the content of the carrier and p-methyl benzenesulfonic acid, Ke Yigen
It is suitably determined according to the loaded catalyst of this field routine, for example, using the total weight of the loaded catalyst as base
Standard, the content of p-methyl benzenesulfonic acid can be 1-50 weight %, preferably 5-50 weight %；The content of the carrier is 50-99 weight
Measure %, preferably 50-95 weight %.
In the present invention, the loaded catalyst can be prepared according to various methods commonly used in the art, only be needed
On the carrier by p-methyl benzenesulfonic acid load.
In a preferred embodiment, in order to make the loaded catalyst of preparation may be repeated utilization, and
Higher reaction raw materials conversion ratio still can be obtained during recycling, the method for preparing loaded catalyst include: by
Carrier, p-methyl benzenesulfonic acid and water are uniformly mixed, and obtained mixture is spray-dried, wherein the carrier is this hair
The above-mentioned spherical mesoporous composite material of attapulgite containing aluminium of bright offer.
It is above-mentioned prepare loaded catalyst during, on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid,
The dosage of p-methyl benzenesulfonic acid can be 1-50 weight %, preferably 5-50 weight %；The dosage of the carrier can be 50-99 weight
Measure %, preferably 50-95 weight %.
The spray drying can be implemented according to conventional mode, such as can carry out in atomizer.It is described spraying dry
Dry condition may include: that temperature is 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/min；Under preferable case,
The condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-13000r/min.
The present invention also provides the loaded catalysts prepared by above-mentioned spray drying process.
The present invention also provides the application of above-mentioned loaded catalyst in the esterification reaction.
The present invention also provides a kind of preparation methods of acid isopropyl, this method comprises: in the presence of a catalyst,
Under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl, which is characterized in that the catalyst is
Loaded catalyst of the present invention.
In the preparation method of the acid isopropyl, there is no particular limitation for the dosage of oleic acid and isopropanol, as long as energy
Enough reactions obtain acid isopropyl, but in order to improve the utilization rate of raw material, under preferable case, mole of oleic acid and isopropanol
Than for 1:0.5-10, preferably 1:1-5.
Also there is no particular limitation for the dosage of the catalyst, can be carried out according to conventional acid isopropyl preparation process
Suitably determine.Under preferable case, relative to the oleic acid of 100 parts by weight, the dosage of the catalyst is 1-15 parts by weight, more excellent
It is selected as 2-14 parts by weight.
In the acid isopropyl preparation process, in order to be more advantageous to the progress of esterification, the reaction preferably exists
It is carried out in there-necked flask, that is, 25~100 DEG C of the reaction temperature.Reaction time can be 1-20 hours, preferably 2-15 hours.
After the preparation method of the acid isopropyl can also be included in esterification, to final reaction mixture
Suction filtration separation is carried out, and isolated solid product will be filtered and be dried in vacuo 1-24 hours at 25-200 DEG C；It is preferred that in 50-
It is dried in vacuo 6-10 hours at 150 DEG C, to recycle catalyst.
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, average molecular weight
Mn is 5800.
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company, Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co., the U.S.
It is carried out on electron microscope；Pore structure parameter analysis is inhaled de- in the nitrogen of the model Autosorb-1 purchased from U.S. Kang Ta company
It is carried out on attached instrument, wherein before being tested, sample is deaerated 4 hours at 200 DEG C；The analysis of reaction product liquid phase ingredient exists
Purchased from being carried out on Agilent company, Britain 7890A/5973N gas chromatograph-mass spectrometer.Aluminium content result is surveyed by XPS Analysis instrument
?.
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio of oleic acid and the selectivity of acid isopropyl are according to following
Formula is calculated.
The conversion ratio (%) of oleic acid=(content of oleic acid in dosage-reaction product of oleic acid) ÷ oleic acid dosage ×
The theoretical yield of selectivity (%)=acid isopropyl actual production ÷ acid isopropyl of 100% acid isopropyl ×
100%
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment for illustrate spherical shape attapulgite containing aluminium mesoporous composite material and loaded catalyst of the invention with
And their preparation method.
(1) the spherical mesoporous composite material of attapulgite containing aluminium is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.69g (0.037mol) ethyl alcohol is added
Into 28ml, the acetic acid and sodium acetate buffer that pH value is 4, stirring is completely dissolved to P123 at 15 DEG C, obtain backward
6g (0.053mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then 2.13g (0.014mol) four is added thereto
Methoxy silane stirs 20h under conditions of 15 DEG C, pH value are 4.5, then obtained solution is transferred in there-necked flask,
At 60 DEG C crystallization for 24 hours, be then filtered and and be washed with deionized 4 times, then filter and obtain with one-dimensional channels diplopore
The filter cake A1 of the meso-porous molecular sieve material of distributed architecture.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and glycerine with weight ratio be
5:1:1 carries out mixing and haptoreaction 2 hours at 30 DEG C, then adjusts pH value to 3, so with the sulfuric acid that concentration is 98 weight %
Obtained reaction mass is filtered afterwards, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel
Filter cake B1.
10g filter cake A1,10g filter cake B1 and 10g attapulgite of above-mentioned preparation is put into togerther (its in 100ml ball grinder
In, the material of ball grinder and abrading-ball is high alumina ceramic, in the high alumina ceramic content of aluminium element be 35 weight %, abrading-ball it is straight
Diameter is 3mm, and quantity is 1, revolving speed 400r/min).Close ball grinder, in ball grinder temperature be 60 DEG C at ball milling 1 hour,
Obtain 30g solid powder；The solid powder is dissolved in 30 grams of deionized waters, at 200 DEG C revolving speed be 12000r/min
Lower spray drying；The product obtained after spray drying is calcined 24 hours at 500 DEG C in Muffle furnace, removed template method obtains
To the 28 grams of spherical shape mesoporous composite material of attapulgite containing aluminium C1 with one-dimensional channels diplopore distributed architecture.According to photoelectron spectroscopy
Analysis as a result, in C1 aluminium content be 18 weight %.
(2) loaded catalyst is prepared
At 25 DEG C, by 30g spherical shape attapulgite containing the aluminium mesoporous composite material C1 prepared in above-mentioned steps (1) and to first
Benzene sulfonic acid is put into togerther in deionized water, and stirring is to dissolving, and the spherical shape mesoporous composite material C1 of attapulgite containing aluminium and to toluene
The weight ratio of sulfonic acid is 50:50, and the molar ratio of deionized water and p-methyl benzenesulfonic acid is 25:1, is in revolving speed at 200 DEG C
It is spray-dried under 12000r/min, obtains loaded catalyst Cat-1.
With XRD, scanning electron microscope and U.S.'s Kang Ta company Atsorb-1 type instrument come to the support type Catalyzed by p-Toluenesulfonic Acid
Agent is characterized.
Fig. 1 is X-ray diffracting spectrum, for the XRD spectra of the spherical mesoporous composite material of attapulgite containing aluminium C1, abscissa
For 2 θ, ordinate is intensity.By the low-angle spectral peak that occurs in XRD spectra it is found that the composite mesoporous material of spherical attapulgite containing aluminium
Expect that C1 has one-dimensional channels diplopore distributed architecture specific to mesoporous material.
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the spherical mesoporous composite material of attapulgite containing aluminium C1.It can by figure
Know, the microscopic appearance of the spherical mesoporous composite material of attapulgite containing aluminium C1 is the Mesoporous Spheres that particle diameter is 30-60 μm.
Fig. 3 is the pore size distribution curve of the spherical mesoporous composite material of attapulgite containing aluminium C1.
Pore structure parameter such as the following table 1 of spherical shape attapulgite containing aluminium mesoporous composite material C1 and loaded catalyst Cat-1
It is shown.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Composite material C1 | 220 | 1.4 | 9,42 | 50 |
| Catalyst Cat-1 | 98 | 0.8 | 3,38 | 50 |
*: the first most probable pore size and the second most probable pore size are separated with comma: it is the first most probable pore size before comma,
It is the second most probable pore size after comma.
It can be seen from the data of upper table 1 the spherical mesoporous composite material of attapulgite containing aluminium load p-methyl benzenesulfonic acid it
Afterwards, specific surface area and pore volume are reduced, this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical containing aluminium
The inside of attapulgite mesoporous composite material.
Comparative example 1
The spherical mesoporous composite material of attapulgite containing aluminium and loaded catalyst are prepared according to the method for embodiment 1, institute is not
With, it is added without attapulgite during preparation is used as the mesoporous composite material of carrier, to be made respectively composite mesoporous
Material D1 and loaded catalyst Cat-D-1.According to XPS Analysis as a result, the content of aluminium is 7 weight % in D1.
Comparative example 2
The spherical mesoporous composite material of attapulgite containing aluminium and loaded catalyst are prepared according to the method for embodiment 1, institute is not
With, it is (big purchased from Jilin with the rodlike mesoporous silicon oxide SBA-15 of identical weight during preparing loaded catalyst
Learn high-tech limited liability company) the filter cake A1 with the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture is replaced, from
And mesoporous composite material D2 and loaded catalyst Cat-D-2 is made respectively.According to XPS Analysis as a result, aluminium in D2
Content be 10 weight %.
Comparative example 3
The spherical mesoporous composite material of attapulgite containing aluminium and loaded catalyst are prepared according to the method for embodiment 1, institute is not
With the material of ball grinder is polytetrafluoroethylene (PTFE), Material quality of grinding balls during preparation is used as the mesoporous composite material of carrier
For agate.To which mesoporous composite material D3 and loaded catalyst Cat-D-3 be made respectively.According to the knot of XPS Analysis
Fruit, the content of aluminium is 4 weight % in D3.
Comparative example 4
The spherical mesoporous composite material of attapulgite containing aluminium and loaded catalyst are prepared according to the method for embodiment 1, institute is not
With, the step of spray drying during preparing loaded catalyst, and only will be to toluene by the method for dipping
Sulfonic acid is supported on the spherical mesoporous composite material of attapulgite containing aluminium, so that loaded catalyst Cat-D-4 be made.
Embodiment 2
The present embodiment for illustrate spherical shape attapulgite containing aluminium mesoporous composite material and loaded catalyst of the invention with
And their preparation method.
(1) the spherical mesoporous composite material of attapulgite containing aluminium is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 5, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
9.12g (0.08mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 3.04g (0.02mol) four is added thereto
Methoxy silane stirs 15h under conditions of 25 DEG C, pH value are 5.5, then obtained solution is transferred in there-necked flask,
Crystallization 10h at 100 DEG C, be then filtered and and be washed with deionized 4 times, then filter and obtain with one-dimensional channels diplopore
The filter cake A2 of the meso-porous molecular sieve material of distributed architecture.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and glycerine with weight ratio be
4:1:1 carries out mixing and haptoreaction 1.5 hours at 40 DEG C, then adjusts pH value to 2 with the sulfuric acid that concentration is 98 weight %,
Then obtained reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel
Filter cake B2.
20g filter cake A2,15g filter cake B2 and 15g attapulgite of above-mentioned preparation is put into togerther (its in 100ml ball grinder
In, the material of ball grinder and abrading-ball is high alumina ceramic, in the high alumina ceramic content of aluminium element be 35 weight %, abrading-ball it is straight
Diameter is 3mm, and quantity is 1, revolving speed 300r/min).Ball grinder is closed, temperature is that ball milling 0.5 is small at 80 DEG C in ball grinder
When, obtain 50g solid powder；The solid powder is dissolved in 36 grams of deionized waters, at 250 DEG C revolving speed be 11000r/
It is spray-dried under min；The product obtained after spray drying is calcined 15 hours at 550 DEG C in Muffle furnace, removed template method,
Obtain 30 grams of spherical shapes mesoporous composite material of attapulgite containing aluminium C2.According to XPS Analysis as a result, in C2 aluminium content
For 10 weight %.
(2) loaded catalyst is prepared
At 25 DEG C, by 20g spherical shape attapulgite containing the aluminium mesoporous composite material C2 prepared in above-mentioned steps (1) and to first
Benzene sulfonic acid is put into togerther in deionized water, and stirring is to dissolving, and the spherical shape mesoporous composite material C2 of attapulgite containing aluminium and to toluene
The weight ratio of sulfonic acid is 95:5, and the molar ratio of deionized water and p-methyl benzenesulfonic acid is 25:1, is in revolving speed at 150 DEG C
It is spray-dried under 13000r/min, obtains loaded catalyst Cat-2.
Pore structure parameter such as the following table 2 of spherical shape attapulgite containing aluminium mesoporous composite material C2 and loaded catalyst Cat-2
It is shown.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Composite material C2 | 154 | 0.9 | 8,41 | 59 |
| Catalyst Cat-2 | 110 | 0.6 | 1.6,23 | 46 |
*: the first most probable pore size and the second most probable pore size are separated with comma: it is the first most probable pore size before comma,
It is the second most probable pore size after comma.
It can be seen from the data of upper table 2 the spherical mesoporous composite material of attapulgite containing aluminium load p-methyl benzenesulfonic acid it
Afterwards, specific surface area and pore volume are reduced, this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical containing aluminium
The inside of attapulgite mesoporous composite material.
Embodiment 3
The present embodiment for illustrate spherical shape attapulgite containing aluminium mesoporous composite material and loaded catalyst of the invention with
And their preparation method.
(1) the spherical mesoporous composite material of attapulgite containing aluminium is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 3, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
5.7g (0.05mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 4.56g (0.03mol) tetramethyl is added thereto
Oxysilane stirs 10h under conditions of 40 DEG C, pH value are 3.5, then obtained solution is transferred in there-necked flask, 40
Crystallization 48h at DEG C, be then filtered and and be washed with deionized 4 times, then filter and obtain with one-dimensional channels diplopore point
The filter cake A3 of the meso-porous molecular sieve material of cloth structure.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and glycerine with weight ratio be
6:1:1 carries out mixing and haptoreaction 3 hours at 20 DEG C, then adjusts pH value to 4, so with the sulfuric acid that concentration is 98 weight %
Obtained reaction mass is filtered afterwards, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel
Filter cake B3.
20g filter cake A3,30g filter cake B3 and 5g attapulgite of above-mentioned preparation is put into togerther (its in 100ml ball grinder
In, the material of ball grinder and abrading-ball is high alumina ceramic, in the high alumina ceramic content of aluminium element be 35 weight %, abrading-ball it is straight
Diameter is 3mm, and quantity is 1, revolving speed 500r/min).Ball grinder is closed, temperature is that ball milling 10 is small at 40 DEG C in ball grinder
When, obtain 55g solid powder；The solid powder is dissolved in 30 grams of deionized waters, at 150 DEG C revolving speed be 13000r/
It is spray-dried under min；The product obtained after spray drying is calcined 70 hours at 450 DEG C in Muffle furnace, removed template method,
Obtain 33 grams of spherical shapes mesoporous composite material of attapulgite containing aluminium C3.According to XPS Analysis as a result, in C3 aluminium content
For 25 weight %.
(2) loaded catalyst is prepared
At 25 DEG C, by 20g spherical shape attapulgite containing the aluminium mesoporous composite material C3 prepared in above-mentioned steps (1) and to first
Benzene sulfonic acid is put into togerther in deionized water, and stirring is to dissolving, and the spherical shape mesoporous composite material C3 of attapulgite containing aluminium and to toluene
The weight ratio of sulfonic acid is 85:15, and the molar ratio of deionized water and p-methyl benzenesulfonic acid is 25:1, is in revolving speed at 250 DEG C
It is spray-dried under 11000r/min, obtains loaded catalyst Cat-3.
Pore structure parameter such as the following table 3 of spherical shape attapulgite containing aluminium mesoporous composite material C3 and loaded catalyst Cat-3
It is shown.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Composite material C3 | 160 | 0.7 | 9,39 | 44 |
| Catalyst Cat-3 | 120 | 0.4 | 7,31 | 56 |
*: the first most probable pore size and the second most probable pore size are separated with comma: it is the first most probable pore size before comma,
It is the second most probable pore size after comma.
It can be seen from the data of upper table 3 the spherical mesoporous composite material of attapulgite containing aluminium load p-methyl benzenesulfonic acid it
Afterwards, specific surface area and pore volume are reduced, this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical containing aluminium
The inside of attapulgite mesoporous composite material.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used to illustrate the application and the system of acid isopropyl of the loaded catalyst provided by the invention
Preparation Method.
Loaded catalyst Cat-1 prepared by embodiment 1 is dried in vacuo 6 hours at 150 DEG C, after being cooled to room temperature,
0.5 gram is weighed, oleic acid 6g, isopropanol 2.8g, Cat-10.5g are sequentially added in there-necked flask, is heated to 75 DEG C, reacts half an hour
Afterwards, it is centrifugated, utilizes gas chromatographic analysis reaction product liquid ingredient, oleic acid conversion 99.9%, acid isopropyl selectivity
100%, yield 73%, solid catalyst Cat-1 is dried in vacuo 6 hours at 150 DEG C, sharp again after recycling after being cooled to room temperature
With.
EXPERIMENTAL EXAMPLE 2-3 and Experimental comparison's example 1-4
Acid isopropyl is prepared according to the method for EXPERIMENTAL EXAMPLE 1, the difference is that using embodiment 2-3 and comparison respectively
The loaded catalyst of example 1-4 preparation replaces the loaded catalyst Cat-1.As a result, the oleic acid being respectively calculated turns
Rate and acid isopropyl selective data are as shown in table 4 below.
Table 4
| Catalyst | The conversion ratio of oleic acid | Acid isopropyl selectivity | |
| EXPERIMENTAL EXAMPLE 1 | Cat-1 | 99.9% | 100% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 98% | 100% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 98% | 100% |
| Experimental comparison's example 1 | Cat-D-1 | 98% | 99% |
| Experimental comparison's example 2 | Cat-D-2 | 97% | 99% |
| Experimental comparison's example 3 | Cat-D-3 | 80% | 99% |
| Experimental comparison's example 4 | Cat-D-4 | 75% | 95% |
EXPERIMENTAL EXAMPLE 4-6 and Experimental comparison's example 5-8
Acid isopropyl is prepared according to the method for EXPERIMENTAL EXAMPLE 1, the difference is that respectively with from EXPERIMENTAL EXAMPLE 1-3
The loaded catalyst Cat-1 is replaced with the catalyst of Experimental comparison's example 1-4 recycling.As a result, the oleic acid being respectively calculated
Conversion ratio and acid isopropyl selective data it is as shown in table 5 below.
Table 5
| Catalyst | The conversion ratio of oleic acid | Acid isopropyl selectivity | |
| EXPERIMENTAL EXAMPLE 4 | The Cat-1 of recycling | 80% | 100% |
| EXPERIMENTAL EXAMPLE 5 | The Cat-2 of recycling | 76% | 100% |
| EXPERIMENTAL EXAMPLE 6 | The Cat-3 of recycling | 71% | 100% |
| Experimental comparison's example 5 | The Cat-D-1 of recycling | 59% | 99% |
| Experimental comparison's example 6 | The Cat-D-2 of recycling | 50% | 99% |
| Experimental comparison's example 7 | The Cat-D-3 of recycling | 45% | 90% |
| Experimental comparison's example 8 | The Cat-D-4 of recycling | 40% | 80% |
Using the composite mesoporous material of the spherical attapulgite containing aluminium of the invention it can be seen from the data of above-mentioned table 4 and 5
Material can significantly improve the conversion of reaction raw materials as loaded catalyst made of carrier in acid isopropyl preparation process
Rate.Moreover, the loaded catalyst can carry out weight when the method by spray drying prepares the loaded catalyst
It is multiple to utilize, and higher reaction raw materials conversion ratio still can be obtained during recycling.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (28)
1. a kind of spherical shape mesoporous composite material of attapulgite containing aluminium, which is characterized in that the spherical shape attapulgite containing aluminium is composite mesoporous
Material contains attapulgite and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, and the spherical shape is concave-convex containing aluminium
The average grain diameter of stick stone mesoporous composite material is 30-60 microns, and specific surface area is 100-600 meters squared per gram, pore volume 0.5-
1.5 mls/g, aperture is in bimodal distribution, and it is bimodal respectively correspond the first most probable pore size and the second most probable pore size, described the
One most probable pore size is 1-9 nanometers, and second most probable pore size is 39-45 nanometers；Have relative to described in 100 parts by weight
The meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, the content of the attapulgite are 1-100 parts by weight；
Wherein, the content of aluminium element is 5-30 weight % in the spherical mesoporous composite material of attapulgite containing aluminium, and the ball
The weight percent of aluminium element is greater than the weight of aluminium element in the attapulgite in the shape mesoporous composite material of attapulgite containing aluminium
Percentage.
2. composite material according to claim 1, wherein aluminium member in the spherical shape mesoporous composite material of attapulgite containing aluminium
The content of element is 10-25 weight %.
3. composite material according to claim 1 or 2, wherein relative to double with one-dimensional channels described in 100 parts by weight
The meso-porous molecular sieve material of pore size distribution structure, the content of the attapulgite are 25-100 parts by weight.
4. composite material according to claim 1 or 2, wherein the content of aluminium element is 1-10 weight in the attapulgite
Measure %.
5. composite material according to claim 1 or 2, wherein the content of aluminium element is 2-8 weight in the attapulgite
Measure %.
6. a kind of method for preparing spherical shape attapulgite containing aluminium mesoporous composite material described in any one of claim 1-5,
Method includes the following steps:
(1) providing meso-porous molecular sieve material or preparation with one-dimensional channels diplopore distributed architecture has one-dimensional channels diplopore point
The filter cake of the meso-porous molecular sieve material of cloth structure, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a, the component b and attapulgite are subjected to mixing and ball milling in high alumina ceramic ball grinder, and by ball
Obtained slurry, is then spray-dried by the solid powder obtained after mill water slurrying, relative to described in 100 parts by weight
The dosage of component a, the component b are 1-200 parts by weight；The dosage of the attapulgite is 1-100 parts by weight；
Wherein, above-mentioned steps make the average grain diameter of the spherical mesoporous composite material of attapulgite containing aluminium be 30-60 microns, than
Surface area is 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal is respectively corresponded
First most probable pore size and the second most probable pore size, first most probable pore size are 1-9 nanometers, second most probable pore size
It is 39-45 nanometers；The content of aluminium element is 5-30 weight % in the spherical shape mesoporous composite material of attapulgite containing aluminium, and described
The weight percent of aluminium element is greater than the weight of aluminium element in the attapulgite in the spherical shape mesoporous composite material of attapulgite containing aluminium
Measure percentage.
7. according to the method described in claim 6, wherein, above-mentioned steps make the composite mesoporous material of the spherical attapulgite containing aluminium
The content of aluminium element is 10-25 weight % in material.
8. method according to claim 6 or 7, wherein in step (3), relative to the component a of 100 parts by weight,
The dosage of the component b is 75-150 parts by weight；The dosage of the attapulgite is 25-100 parts by weight.
9. method according to claim 6 or 7, wherein in step (1), preparation has one-dimensional channels diplopore distribution knot
The process of the filter cake of the meso-porous molecular sieve material of structure includes: in the presence of template, trimethylpentane and ethyl alcohol, by four methoxies
Base silane is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtering.
10. according to the method described in claim 9, wherein, template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane rub
You are than being 1:100-500:200-500:50-200.
11. according to the method described in claim 9, wherein, template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane rub
You are than being 1:180-400:250-400:70-150.
12. according to the method described in claim 9, wherein, the template is triblock copolymer polyoxyethylene-polyoxy third
Alkene-polyoxyethylene；The acid agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6；Tetramethoxy-silicane is contacted with sour agent
Condition include: temperature be 10-60 DEG C, the time be 10-72 hours, pH value 1-7；The condition of the crystallization includes: that temperature is
30-150 DEG C, the time is 10-72 hours.
13. method according to claim 6 or 7, wherein in step (2), the process for preparing the filter cake of silica gel includes:
Waterglass is contacted with inorganic acid and glycerine, and the mixture obtained after contact is filtered.
14. according to the method for claim 13, wherein the condition that waterglass is contacted with inorganic acid and glycerine includes: temperature
Degree is 10-60 DEG C, and the time is 1-5 hours, pH value 2-4；The inorganic acid is one of sulfuric acid, nitric acid and hydrochloric acid or more
Kind.
15. method according to claim 6 or 7, wherein in step (3), the condition of the ball milling includes: high alumina pottery
The revolving speed of porcelain media is 300-500r/min, and the temperature in high alumina ceramic ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-
100 hours；The condition of the spray drying includes: 100-300 DEG C of temperature, revolving speed 10000-15000r/min.
16. method according to claim 6 or 7, wherein the component a is with one-dimensional channels diplopore distributed architecture
The filter cake of meso-porous molecular sieve material, the component b are the filter cake of silica gel, the method also includes: the spray drying in step (3)
After process, the removed template method from the product that spray drying obtains.
17. according to the method for claim 16, wherein the condition of the removed template method includes: that temperature is 300-600
DEG C, the time is 10-80 hours.
18. a kind of loaded catalyst, which contains the p-methyl benzenesulfonic acid of carrier and load on the carrier, feature
It is, the carrier is the spherical shape mesoporous composite material of attapulgite containing aluminium described in any one of claim 1-5.
19. catalyst according to claim 18, wherein on the basis of the total weight of the loaded catalyst, to first
The content of benzene sulfonic acid is 1-50 weight %；The content of the carrier is 50-99 weight %.
20. catalyst according to claim 18, wherein on the basis of the total weight of the loaded catalyst, to first
The content of benzene sulfonic acid is 5-50 weight %；The content 50-95 weight % of the carrier.
21. a kind of method for preparing loaded catalyst described in any one of claim 18-20, this method comprises: will
Carrier, p-methyl benzenesulfonic acid and water are uniformly mixed, and obtained mixture is spray-dried, wherein the carrier is right
It is required that spherical shape attapulgite containing aluminium mesoporous composite material described in any one of 1-5.
22. according to the method for claim 21, wherein right on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid
The dosage of toluenesulfonic acid is 1-50 weight %；The dosage of the carrier is 50-99 weight %.
23. according to the method for claim 21, wherein right on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid
The dosage of toluenesulfonic acid is 5-50 weight %；The dosage of the carrier is 50-95 weight %.
24. the application of loaded catalyst in the esterification reaction described in any one of claim 18-20.
25. a kind of preparation method of acid isopropyl, wherein this method comprises: in the presence of a catalyst, in esterification
Under the conditions of, contact oleic acid and isopropanol, to obtain acid isopropyl, which is characterized in that the catalyst is claim 18-
Loaded catalyst described in any one of 20.
26. preparation method according to claim 25, wherein the molar ratio of oleic acid and isopropanol is 1:0.5-10.
27. preparation method according to claim 25, wherein relative to the oleic acid of 100 parts by weight, the use of the catalyst
Amount is 1-15 parts by weight.
28. preparation method according to claim 25, wherein relative to the oleic acid of 100 parts by weight, the use of the catalyst
Amount is 2-14 parts by weight.
Priority Applications (1)
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