CN109499586A - Rare earth modified solid super acid catalyst and preparation method thereof - Google Patents
Rare earth modified solid super acid catalyst and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 68
- 239000007787 solid Substances 0.000 title claims abstract description 53
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000003930 superacid Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- -1 rare earth ion Chemical class 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 17
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 21
- 229910052593 corundum Inorganic materials 0.000 description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- BSYNRYMUTXBXSQ-FOQJRBATSA-N 59096-14-9 Chemical compound CC(=O)OC1=CC=CC=C1[14C](O)=O BSYNRYMUTXBXSQ-FOQJRBATSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 229910016287 MxOy Inorganic materials 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 1
- 208000006820 Arthralgia Diseases 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000017897 Carcinoma of esophagus Diseases 0.000 description 1
- 206010009944 Colon cancer Diseases 0.000 description 1
- 208000000461 Esophageal Neoplasms Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000000702 anti-platelet effect Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 210000000664 rectum Anatomy 0.000 description 1
- 201000001275 rectum cancer Diseases 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 208000004371 toothache Diseases 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
This application involves a kind of rare earth modified solid super acid catalysts and preparation method thereof.The rare earth modified solid super acid catalyst includes that complex carrier, the sulfate radical being incorporated on complex carrier and the rare earth ion with complex carrier doping, complex carrier are combined by silica and aluminum oxide.Above-mentioned rare earth modified solid super acid catalyst, by introducing rare earth element in solid super-strong acid, the chemical state for changing solid super-strong acid surface atom improves solid super-strong acid surface-element positive polarization degree and electron-withdrawing ability, facilitates the catalytic activity and service life that improve catalyst.
Description
Technical field
The present invention relates to catalysis technical fields, more particularly to rare earth modified solid super acid catalyst and its preparation side
Method.
Background technique
Acetylsalicylic acid is a kind of time-honored analgesic-antipyretic, is born in 1899, is historical three big classical
One of drug, for curing cold, generating heat, have a headache, have a toothache, arthralgia, rheumatism etc..Its purposes is constantly found in recent years: right
Crops have the special efficacies such as good volume increase, drought resisting, it may also be used for the kinds cancers such as breast cancer, cancer of the esophagus, carcinoma of the colon and rectum
Prevention and treatment, also there is anti-platelet aggregation effect, then cause the great interest of people again, also increasingly to its demand
Increase.In view of the extensive use of acetylsalicylic acid, the novel process of research synthesis acetylsalicylic acid, to improve its yield and product
Matter has practical significance.
In the production of traditional acetylsalicylic acid, salicylic acid and aceticanhydride carry out reaction at 80 DEG C~90 DEG C and generate acetyl salicylic
Acid, the reaction time 2 hours or so, energy consumption was larger.Traditional sulfuric acid catalysis method synthesizes acetylsalicylic acid, although classics side
Method, technical maturity, but yield, generally between 60%~70%, side reaction is more, equipment seriously corroded, pollutes environment.Using
Hydrochloric acid is swift in response as catalyst, the method, and yield is higher, but its low boiling point, volatile, and it is unstable to provide proton acid concentration,
Product quality is influenced, has corrosion to equipment, working environment is poor.Oxalic Acid Method reaction is slowly gentle, and the reaction time is long, material consumption, energy consumption
Height, and by-product is more.The generally existing some disadvantages of liquid acid catalyst, such as it is not easy to separate with system after reaction, equipment
Perishable aging, energy consumption is high, and environment easy to pollute etc., these problems attract attention.
In recent years, since basic power source price rises steadily, the reaction time, more long then energy consumption was bigger, and cost is higher.From close
Several years research tendencies are seen, in the main base of the emphasis of research during salicylic acid and anhydride reaction, by adding different urge
Agent, so that reaction is easier to carry out, the time is shorter, and energy consumption is less, and product quality is more preferable.
SO4 2-/MxOyType solid super-strong acid, which is that one kind is convenient, easily separated with preparation, to be regenerated and reuses, is environmental-friendly
The advantages that new catalyst, because its organic acid catalysis reaction in extensive use due to always be research hotspot.SO4 2-/MxOy
Type solid super-strong acid is that a kind of novel green having a extensive future is urged there are many excellent performance not available for traditional catalyst
Change material.SO4 2-/MxOyThere is also some disadvantages for type solid super acid catalyst, such as the easy carbon distribution of such catalyst, thermal stability
Difference, active component are easy to run off and inactivate, and these problems all constrain its application industrially.In order to improve catalyst performance
And the service life, its use scope is expanded, to SO4 2-/MxOyThe study on the modification of type solid super-strong acid is particularly important.
Summary of the invention
Based on this, it is necessary to provide a kind of rare earth modified solid superacid as catalyst with preferable catalytic performance and service life
Agent, concrete scheme are as follows:
A kind of rare earth modified solid super acid catalyst, including complex carrier, the sulfuric acid being incorporated on the complex carrier
Root and the rare earth ion adulterated with the complex carrier, the complex carrier are combined by silica and aluminum oxide.
Above-mentioned rare earth modified solid super acid catalyst R3+/SO4 2-/SiO2-Al2O3, complex carrier SiO2-Al2O3It provides
Bigger specific surface area facilitates the SO on steady oxide surface4 2-, it can effectively change the acid site intensity of catalyst surface, from
And improve its catalytic performance.In addition, by solid super-strong acid SO4 2-/SiO2-Al2O3Middle introducing rare earth element changes solid
The chemical state of body super acids surface atom improves solid super-strong acid surface-element positive polarization degree and electron-withdrawing ability, has
Help improve the catalytic activity and service life of catalyst.
The rare earth ion is selected from La in one of the embodiments,3+、Y3+、Eu3+And Ce3+At least one of.
The specific surface area of the rare earth modified solid super acid catalyst is 3500cm in one of the embodiments,2/cm3
~3600cm2/cm3
The partial size of the rare earth modified solid super acid catalyst is 20 μm~30 μm in one of the embodiments,.
The application also provides a kind of preparation method of rare earth modified solid super acid catalyst, and concrete scheme is as follows:
The preparation method of rare earth modified solid super acid catalyst described in any of the above embodiments, comprising the following steps:
Aluminum sulfate solution, hydrochloric acid and sodium silicate solution are mixed, adjusting pH is 5~6, be filtered, washed, dry after having reacted,
Calcining, obtains the complex carrier；
The complex carrier is immersed in rare-earth salt solution, calcines, obtains rare earth ion doped complex carrier；
The rare earth ion doped complex carrier is impregnated in sulfuric acid solution, rare earth modified solid super-strong acid is obtained and urges
Agent.
Described the step of mixing aluminum sulfate solution, hydrochloric acid and sodium silicate solution in one of the embodiments, specifically:
It will be mixed again with the sodium silicate solution after the aluminum sulfate solution and mixed in hydrochloric acid.
In one of the embodiments, in the calcining, in the step of obtaining the complex carrier, the temperature of the calcining
It is 500 DEG C~600 DEG C, the time of the calcining is 3~5 hours.
It is described in the step of obtaining rare earth ion doped complex carrier in one of the embodiments, in the calcining
The temperature of calcining is 500 DEG C~600 DEG C, and the time of the calcining is 3~5 hours.
Detailed description of the invention
Fig. 1 is La prepared by embodiment 13+/SO4 2-/SiO2-Al2O3FT-IR spectrogram；
Fig. 2 is La prepared by embodiment 13+/SO4 2-/SiO2-Al2O3XRD spectra.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
The rare earth modified solid super acid catalyst of one embodiment, including complex carrier, be incorporated on complex carrier
Sulfate radical and with complex carrier doping rare earth ion, wherein complex carrier it is compound by silica and aluminum oxide and
At.
Above-mentioned rare earth modified solid super acid catalyst can indicate are as follows: R3+/SO4 2-/SiO2-Al2O3, wherein R3+It is dilute
Native ion.
Further, rare earth ion is selected from La3+、Y3+、Eu3+And Ce3+At least one of.
Further, the specific surface area of above-mentioned rare earth modified solid super acid catalyst is 3500cm2/cm3~3600cm2/
cm3；Further, the specific surface area of above-mentioned rare earth modified solid super acid catalyst is 3521.783cm2/cm3。
Further, the partial size of rare earth modified solid super acid catalyst is 20 μm~30 μm；Further, above-mentioned dilute
The partial size of land reform solid super acid catalyst is 25.61 μm.
Above-mentioned rare earth modified solid super acid catalyst R3+/SO4 2-/SiO2-Al2O3, complex carrier SiO2-Al2O3It provides
Bigger specific surface area facilitates the SO on steady oxide surface4 2-, it can effectively change the acid site intensity of catalyst surface, from
And improve its catalytic performance.In addition, by solid super-strong acid SO4 2-/SiO2-Al2O3Middle introducing rare earth element changes solid
The chemical state of body super acids surface atom improves solid super-strong acid surface-element positive polarization degree and electron-withdrawing ability, has
Help improve the catalytic activity and service life of catalyst.
The preparation method of the rare earth modified solid super acid catalyst of one embodiment, include the following steps S110~
S130:
S110, by aluminum sulfate (Al2(SO4)3) solution, hydrochloric acid (HCl) solution and sodium metasilicate (Na2SiO3·9H2O) solution is mixed
It closes, adjusting pH is 6, is filtered, washed, dries, calcines after having reacted, obtains complex carrier SiO2-Al2O3。
In the present embodiment, the step of aluminum sulfate solution, hydrochloric acid solution and sodium silicate solution being mixed specifically: by sulphur
It is mixed again with sodium silicate solution after sour aluminum solutions and mixed in hydrochloric acid.
Wherein, the concentration of aluminum sulfate solution is 0.5mol/L, and the concentration of hydrochloric acid is 4mol/L, and the quality of sodium silicate solution is dense
Degree is 30%.
Further, Na2SiO3·9H2O、Al2(SO4)3Mass ratio with HCl is 1:(1~3): (1~2).
Further, it is sodium hydroxide solution that reagent used in pH is adjusted in step S110.
Further, the method for filtering is to filter.The method of washing are as follows: alcohol is washed after washing.
Further, dry method is drying.
Further, the temperature calcined in step S110 is 500 DEG C~600 DEG C, and the time of calcining is 3~5 hours.
S120, above-mentioned complex carrier is immersed in rare-earth salt solution, calcines, obtains rare earth ion doped compound load
Body.
Wherein, the mass concentration of rare-earth salt solution is 2% or so.
Further, the temperature calcined in step S120 is 500 DEG C~600 DEG C, and the time of calcining is 3~5 hours
S130, above-mentioned rare earth ion doped complex carrier is impregnated in sulfuric acid solution, obtains rare earth modified solid
Super acidic catalyst.
Wherein, the mass concentration of sulfuric acid solution is 75% or so.
Further, the time of rare earth ion doped complex carrier dipping is 15 hours or so.
The preparation method of above-mentioned rare earth modified solid super acid catalyst first prepares complex carrier using the precipitation method, then mixes
Miscellaneous rare earth ion is modified, is impregnated after calcining again using the concentrated sulfuric acid, obtains rare earth modified super acids solid catalyst, partial size compared with
Small, specific surface area is larger, and structure stable homogeneous, catalytic performance is good, lasts a long time.
The following are specific embodiments
Embodiment 1
(1)SiO2-Al2O3Preparation
It takes the aluminum sulfate of a certain amount of 0.5mol/L that appropriate 4mol/L hydrochloric acid is added and is uniformly mixed, it is 30% that concentration, which is added,
Sodium metasilicate and be uniformly mixed, wherein reactant Na2SiO3·9H2O:Al2(SO4)3: the ratio between amount of HCl three's substance is 1:2:
1.1, adjusting pH with diluted sodium hydroxide solution is 6, is filtered after reacting 1h, and washing, ethyl alcohol are washed, and is put into Muffle furnace after drying, 550 DEG C
4h is calcined, complex carrier SiO is made2-Al2O, it is spare.
(2) rare earth La3+Modified SO4 2-/SiO2-Al2O3The preparation of solid super-strong acid
With complex carrier SiO2-Al2O3For presoma, the rare earth La that mass concentration is 2% is adulterated3+It is modified, it is forged at 550 DEG C
4h is burnt, then the concentrated sulfuric acid of mass concentration 75% is used to impregnate for 15h, obtains rare earth modified solid super-strong acid La3+/SO4 2-/SiO2-
Al2O3, FT-IR spectrogram and XRD spectra are as shown in Figure 1.
Through detecting, the La of the preparation of embodiment 13+/SO4 2-/SiO2-Al2O3Partial size be 25.261 μm, specific surface area is
3521.783cm2/cm3。
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, unlike, comparative example 1 is first by complex carrier SiO2-Al2O3Dipping
In concentrated sulfuric acid, then mass concentration is adulterated as 2% rare earth La3+Modified, calcining obtains rare earth modified solid superacid as catalyst
Agent.
Through detecting, the La of the preparation of comparative example 13+/SO4 2-/SiO2-Al2O3Partial size be 29.165 μm, specific surface area is
2889.568cm2/cm3。
Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, unlike, first by complex carrier SiO in comparative example 22-Al2O3Dipping
In concentrated sulfuric acid, it calcines, then adulterates the rare earth La that mass concentration is 2%3+It is modified, obtain rare earth modified solid superacid as catalyst
Agent.
Through detecting, the La of the preparation of comparative example 23+/SO4 2-/SiO2-Al2O3Partial size be 26.305 μm, specific surface area is
3241.251cm2/cm3。
Comparative example 3
Comparative example 3 is substantially the same manner as Example 1, unlike, first by complex carrier SiO in comparative example 32-Al2O3First mix
The rare earth La that impurity level concentration is 2%3+It is modified, then impregnate in concentrated sulfuric acid, calcining, then obtain rare earth modified solid super-strong acid and urge
Agent.
Through detecting, the La of the preparation of comparative example 23+/SO4 2-/SiO2-Al2O3Partial size be 30.793 μm, specific surface area is
3446.930cm2/cm3。
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (8)
1. a kind of rare earth modified solid super acid catalyst, which is characterized in that including complex carrier, be incorporated in the complex carrier
On sulfate radical and rare earth ion with complex carrier doping, the complex carrier answered by silica and aluminum oxide
It closes.
2. rare earth modified solid super acid catalyst according to claim 1, which is characterized in that the rare earth ion is selected from
La3+、Y3+、Eu3+And Ce3+At least one of.
3. rare earth modified solid super acid catalyst according to claim 1 or 2, which is characterized in that described rare earth modified
The specific surface area of solid super acid catalyst is 3500cm2/cm3~3600cm2/cm3。
4. rare earth modified solid super acid catalyst according to claim 1 or 2, which is characterized in that described rare earth modified
The partial size of solid super acid catalyst is 20 μm~30 μm.
5. a kind of preparation method of the described in any item rare earth modified solid super acid catalysts of Claims 1 to 4, feature exist
In, comprising the following steps:
Aluminum sulfate solution, hydrochloric acid and sodium silicate solution are mixed, adjusting pH is 5~6, it is filtered, washed, dries, calcines after having reacted,
Obtain the complex carrier；
The complex carrier is immersed in rare-earth salt solution, calcines, obtains rare earth ion doped complex carrier；
The rare earth ion doped complex carrier is impregnated in sulfuric acid solution, the rare earth modified solid super-strong acid is obtained and urges
Agent.
6. the preparation method of rare earth modified solid super acid catalyst according to claim 5, which is characterized in that described to incite somebody to action
The step of aluminum sulfate solution, hydrochloric acid and sodium silicate solution mix specifically: by after the aluminum sulfate solution and mixed in hydrochloric acid again with
The sodium silicate solution mixing.
7. the preparation method of rare earth modified solid super acid catalyst according to claim 5 or 6, which is characterized in that
The calcining, in the step of obtaining the complex carrier, the temperature of the calcining is 500 DEG C~600 DEG C, the time of the calcining
It is 3~5 hours.
8. the preparation method of rare earth modified solid super acid catalyst according to claim 5 or 6, which is characterized in that
The calcining, in the step of obtaining rare earth ion doped complex carrier, the temperature of the calcining is 500~600 DEG C, described to forge
The time of burning is 3~5 hours.
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| CN201811480646.9A CN109499586A (en) | 2018-12-05 | 2018-12-05 | Rare earth modified solid super acid catalyst and preparation method thereof |
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| CN201811480646.9A CN109499586A (en) | 2018-12-05 | 2018-12-05 | Rare earth modified solid super acid catalyst and preparation method thereof |
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