CN104549379B - Sulfated zirconium phosphonate solid strong acid porous material and preparation method - Google Patents
Sulfated zirconium phosphonate solid strong acid porous material and preparation method Download PDFInfo
- Publication number
- CN104549379B CN104549379B CN201310491944.9A CN201310491944A CN104549379B CN 104549379 B CN104549379 B CN 104549379B CN 201310491944 A CN201310491944 A CN 201310491944A CN 104549379 B CN104549379 B CN 104549379B
- Authority
- CN
- China
- Prior art keywords
- porous material
- acid
- macropore
- diameter
- propoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a sulfated zirconium phosphonate solid strong acid porous material. The granule diameter of the material is from tens of microns to hundreds of microns, the material is in a mesoporous-macropore structure, the pore diameter of a macropore is 300-500nm, a pore wall of which the diameter is 1.6-2.2nm between macropores is in a mesoporous structure, the specific surface area is 400-650m＜2＞/g, and the exchange capacity of a hydrogen ion is 5.4-6.6mmol/g. The porous material has the advantages that the acidity is strong, and the porous material has a higher actual industrial production value.
Description
Technical field
The present invention relates to solid strong acid material and preparation method thereof, more particularly to having mesopore-macropore structure
Sulfonated phosphonic acids zirconium solid strong acid porous material and its preparation.
Background technology
In recent years, increasingly stricter, the chemical work of the continuous enhancing with people's environmental consciousness and environmental protection legislation demands
Pollution problem in industry is increasingly taken seriously.Acid catalyst is widely used in catalytic field, traditional liquid
Acid catalyst such as h2so4, hcl, h3po4Extensive application, create substantial amounts of waste liquid, exist that equipment corrosion is serious and catalysis
Agent is difficult with reactants separate, and chemical technology is difficult to the shortcomings of continuously produce.Solid acid catalyst, due to selectivity
High, side reaction is few, easily and reactants separate, reusable, not etching apparatus, free from environmental pollution the advantages of, liquid can be substituted
Body acid, is an important channel realizing environmental friendly catalysis technique.
Porous Catalyst, is easy to mass transfer because its specific surface area is big and is rich in permeability in the material, can improve acid and urge
Change efficiency.Cation exchange resin catalyst as a kind of industrialized macropore solid acid catalyst, etherificate, alkylation,
Extensively apply in the organic catalytic reactions such as polyreaction, but the use temperature of resin catalyst typically below 120 DEG C, when anti-
When answering temperature to reach 140-150 DEG C, easily lose sulfonic acid group and inactivate, which limits the range of application of resin catalyst.Separately
One class is micro porous molecular sieve by extensively industrialized solid acid catalyst, is widely used in oil catalysis because its heat resisting temperature is high
The pyroreactions such as cracking, but not ideal for middle low-temp reaction (- 200 DEG C of room temperature) catalysis activity.In order to improve microporous molecular
Sieve, in the catalysis activity of middle low temperature, typically as carrier, then loads heteropoly acid (cn1289641a) or al2o3
(cn101298053a) etc., but the catalyst of these support types equally exists active sites the problems such as be easy to run off.Phosphoric acid is modified
Metal-oxide and phosphate cellular material receive much concern always, but their Surface acidity is generally all little.
Content of the invention
The material with high permeability, multiple dimensioned pore structure and high-ratio surface is in Industrial Catalysis field and other practical application
Play an important role.Although there is the micropores such as the molecular sieve of homogeneous regular pore structure or mesoporous material in catalysis, absorption and divide
From etc. aspect be widely used, but practical application generally requires micropore and mesoporous material has point shape of different length size
Multichannel pore structure, to obtain highly effective function.In mesoporous material introduce macroporous structure, this containing inherent with
The pore system of mesoporous intercommunication macroporous structure can be with the diffusion of intensified response thing and product molecule, and effectively transmission reaction species are to skeleton
Active sites, improve catalysis activity.
The present inventor is by substantial amounts of test it was unexpectedly observed that inducing self assembly by simple surfactant
Method and sulfonic acid funtionalized are processed, and can prepare the sulfonated phosphonic acids zirconium multi-stage porous catalysis material with mesopore-macropore, it compares table
Face is high, and hydrion exchange capacity is big (may be up to 6.6mmol/g), acid strength can with sulfuric acid phase when (Hami paricular value is less than-
11.35) acid catalyzed reaction of middle low temperature, can be applied to as strong solid acid catalyst.
Therefore, it is an object of the invention to provide a kind of sulfonated phosphonic acids zirconium of novelty for solid acid catalysis reaction is solid
Body strong acid porous material simultaneously provides its preparation method.
A kind of sulfonated phosphonic acids zirconium solid strong acid porous material that the present invention provides is it is characterised in that the granule of this material is straight
Footpath has mesopore-macropore structure, macropore diameter 300-500nm, the hole wall between macropore is diameter 1.6- tens to hundreds of micron
The meso-hole structure of 2.2nm, specific surface area 400-650m2/ g, hydrion exchange capacity is 5.4-6.6mmol/g.
The solid strong acid porous material that the present invention provides, preferably in the case of, pore volume is 0.45-0.60cm3/ g, specific surface
Amass as 450-620m2/ g, the hole wall between described macropore is the meso-hole structure of diameter 1.8-2.1nm.
The present invention still further provides the preparation method of above-mentioned sulfonated phosphonic acids zirconium solid strong acid porous material, and it is special
Levy and be to comprise the steps:
1) surfactant spermaceti polyoxyethylenated alcohol and HEDP are dissolved in water, in temperature
Add zirconium iso-propoxide, mix homogeneously under 20-80 DEG C of constant temperature, obtain constituent mass ratio for zirconium iso-propoxide: 1- hydroxyl Asia second
Base -1,1- di 2 ethylhexyl phosphonic acid: water: spermaceti polyoxyethylenated alcohol=(0.5-1.5): (0.3-2): (15-100): the mixing of (0.2-1)
Thing；
2) mixture is proceeded to reactor crystallization 10-120 hour at 40-120 DEG C；
3) after crystallization product filters, with Soxhlet soxhlet extraction process through ethanol extraction, extraction product and volume ratio 1:(0.5
～2) anhydrous pyridine contacts with the mixed solution of chlorosulfonic acid at least 1 hour, and products therefrom is again through filtering, washing and be dried to obtain
Porous material.
The method of the present invention, wherein, temperature described in step 1) is preferably 40～60 DEG C, wherein, described addition isopropyl
Alcohol zirconium is preferably carried out in the way of Deca.The mass ratio of described mixture is preferably zirconium iso-propoxide: 1- hydroxy ethylene -1,
1- di 2 ethylhexyl phosphonic acid: water: spermaceti polyoxyethylenated alcohol=(1-1.5): (1-1.8): (20-60): (0.5-0.8).
The method of the present invention, wherein, step 2) described in crystallization preferably carry out 24～72 hours at 60～100 DEG C.
In the method for the present invention, in the anhydrous pyridine and the mixed solution of chlorosulfonic acid described in step 3), anhydrous pyridine and chlorine
The volume ratio of sulfonic acid is 1:(0.5～2), preferably 1:1, the mixed solution of described anhydrous pyridine and chlorosulfonic acid with feed intake
The ratio of HEDP be 5～30:1, wherein, mixed solution in terms of milliliter, 1- hydroxy ethylene -1,
1- di 2 ethylhexyl phosphonic acid is in gram.Described contact, its time of contact is at least 1 hour, preferably at least 5 hours.
What the present invention provided has following features:
1. the porous material that the present invention provides, material specific surface is high, has hierarchical porous structure；Organic phospho acid content can be relatively
Interior change on a large scale, thus modulation acid amount, and distribution in pore structure for the organic phospho acid, improve active sites acid site in skeleton
Position；
2. the experiment such as proportioning raw materials, the hydrolysis rate controlling zirconium iso-propoxide, change crystallization temperature in being tested by regulation
The distribution of condition pore size controlling and specific surface；
3. there is high mechanical stability and hydrothermal stability；
4. regeneration is simple, and acid catalytic property is good.
Specific embodiment
Below by embodiment, the present invention is further illustrated, but content not thereby limiting the invention.
In embodiment, used reagent in addition to special instructions, is chemically pure reagent.
In an embodiment, sample specific surface area, pore volume, aperture are measured by nitrogen absorption under low temperature-desorption method.
Embodiment 1
1.0 grams of 1- hydroxy ethylene -1,1- di 2 ethylhexyl phosphonic acid (being abbreviated as hedp) and 0.3 gram of spermaceti polyoxyethylenated alcohol are added
To in 25 milliliters of water, after stirring 1 hour at 35 DEG C, be slowly added dropwise zirconium iso-propoxide (purity: 99.9%, the lark prestige limited public affairs of science and technology
Department) 1.0 grams, continue low rate mixing 1 hour, load in reactor in 80 DEG C of crystallization 24 hours.Solid product after filtering, in rope
Extracted 24 hours with ethanol in family name's extraction device.It is then added to anhydrous pyridine (ar, the Tianjin health of 10 milliliters of volume ratios 1:1
Coudé Science and Technology Ltd.) and the mixed solution of chlorosulfonic acid (ar, Gracia (Chengdu) chemical technology company limited commodity) in,
It is slowly stirred 5 hours, refilter, wash, being dried.
The bet specific surface area of material is 610m2/ g, pore volume is 0.55cm3/ g, macropore diameter is distributed in 300-500nm, is situated between
Hole aperture is 1.9nm, and proton exchange capacity is 6.6mmol/g.
Embodiment 2
Using the preparation process of embodiment 1, add 1.5 grams of zirconium iso-propoxides, 60 DEG C of crystallization 48 hours.
The bet specific surface area of the material obtaining is 480m2/ g, pore volume is 0.45cm3/ g, mesoporous pore size 1.8nm, macropore is straight
Mainly in 300-500nm, hydrion exchange capacity is 5.8mmol/g for footpath distribution.
Embodiment 3
Using the preparation process of embodiment 1,2.0 grams of hedp and 1.0 gram of spermaceti polyoxyethylenated alcohol are added to 60 milliliters of water
In, 1.5 grams of zirconium iso-propoxide, 80 DEG C of crystallization 24 hours.
The bet specific surface area of the material obtaining is 550m2/ g, pore volume is 0.5cm3/ g, mesoporous pore size is 2.1nm, macropore hole
Footpath is 300-500nm, and hydrion exchange capacity is 6.0mmol/g.
Embodiment 4
Using the preparation process of embodiment 1,1.2 grams of hedp and 0.5 gram of spermaceti polyoxyethylenated alcohol are added in 30 grams of water,
1.0 grams of zirconium iso-propoxide, 60 DEG C of crystallization 72 hours.
The bet specific surface area of the material obtaining is 540m2/ g, pore volume is 0.48cm3/ g, mesoporous pore size size is 2.0nm,
Macropore diameter is 300-500nm, and proton exchange capacity is 5.4mmol/g.
Embodiment 5
Using the preparation process of embodiment 1,1.8 grams of hedp and 0.6 gram of spermaceti polyoxyethylenated alcohol are added in 40 grams of water,
1.0 grams of zirconium iso-propoxide, 80 DEG C of crystallization 36 hours.
The bet specific surface area of the material obtaining is 485m2/g；Pore volume is 0.6cm3/ g, mesoporous pore size size is 1.9nm, greatly
Hole aperture is 300-500nm, and proton exchange capacity is 6.4mmol/g.
Claims (9)
1. a kind of sulfonated phosphonic acids zirconium solid strong acid porous material, the particle diameter of this material, has to hundreds of micron tens
Mesopore-macropore structure, macropore diameter 300-500nm, the hole wall between macropore is the meso-hole structure of diameter 1.6-2.2nm, specific surface
Long-pending 400-650m2/ g, hydrion exchange capacity is 5.4-6.6mmol/g, and this sulfonated phosphonic acids zirconium solid strong acid porous material is
With comprise the steps method preparation:
(1) surfactant spermaceti polyoxyethylenated alcohol and HEDP are dissolved in water, in temperature 20-
Add zirconium iso-propoxide, mix homogeneously under 80 DEG C of constant temperature, obtain constituent mass ratio for zirconium iso-propoxide: 1- hydroxy ethylene-
1,1- di 2 ethylhexyl phosphonic acid: water: spermaceti polyoxyethylenated alcohol=(0.5-1.5): (0.3-2): (15-100): the mixture of (0.2-1)；
(2) by mixture at 40-120 DEG C of closed reactor crystallization 10-120 hour；
(3), after crystallization product filters, extracted through ethanol with Soxhlet soxhlet extraction process, extraction product and volume ratio 1:(0.5～
2) anhydrous pyridine contacts with the mixed solution of chlorosulfonic acid at least 1 hour, and products therefrom is again through filtering, washing and be dried to obtain many
Porous materials.
2. according to claim 1 porous material it is characterised in that its pore volume 0.45-0.60cm3/g.
3. according to the porous material of claim 1, wherein, described specific surface area is 450-620m2/g.
4. according to the porous material of claim 1, wherein, the hole wall between described macropore is the mesoporous knot of diameter 1.8-2.1nm
Structure.
5. according to the porous material of claim 1, wherein, step 1) described in temperature be 40～60 DEG C.
6. according to the porous material of claim 1, wherein, step 1) described in mixture mass ratio be zirconium iso-propoxide: 1- hydroxyl
Base ethylidene -1,1- di 2 ethylhexyl phosphonic acid: water: spermaceti polyoxyethylenated alcohol=(1-1.5): (1-1.8): (20-60): (0.5-0.8).
7. according to the porous material of claim 1, wherein, step 2) described in crystallization be that to carry out 24～72 at 60～100 DEG C little
When.
8. according to the porous material of claim 1, wherein, step 2) described in anhydrous pyridine and chlorosulfonic acid mixed solution in,
The volume ratio of anhydrous pyridine and chlorosulfonic acid is 1:1.
9. according to the porous material of claim 1, wherein, step 3) described in contact, its time of contact is at least 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310491944.9A CN104549379B (en) | 2013-10-18 | 2013-10-18 | Sulfated zirconium phosphonate solid strong acid porous material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310491944.9A CN104549379B (en) | 2013-10-18 | 2013-10-18 | Sulfated zirconium phosphonate solid strong acid porous material and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549379A CN104549379A (en) | 2015-04-29 |
| CN104549379B true CN104549379B (en) | 2017-01-18 |
Family
ID=53067084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310491944.9A Active CN104549379B (en) | 2013-10-18 | 2013-10-18 | Sulfated zirconium phosphonate solid strong acid porous material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549379B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101036873A (en) * | 2007-01-23 | 2007-09-19 | 南开大学 | Organic phosphonium transition metal salt graded hole material preparing method and the application |
| CN101402790A (en) * | 2008-11-14 | 2009-04-08 | 山东理工大学 | Sulfonation phenylphosphonic acid zirconium doping proton exchanging film and method of producing the same |
| CN101475589A (en) * | 2009-01-19 | 2009-07-08 | 南开大学 | Preparation and use of mesoporous-macroporous structure aluminum organophosphonate material |
| CN101708459A (en) * | 2009-12-03 | 2010-05-19 | 南开大学 | Method for preparing ordered mesoporous organic titanium phosphonate hybrid material and application thereof |
| CN102019203A (en) * | 2010-11-23 | 2011-04-20 | 南开大学 | Method for fast synthesizing mesoporous solid acid catalyst immobilized with sulfonic acid |
| CN102671697A (en) * | 2012-05-07 | 2012-09-19 | 天津神能科技有限公司 | Preparation method and application of mesoporous solid acid catalyst |
-
2013
- 2013-10-18 CN CN201310491944.9A patent/CN104549379B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101036873A (en) * | 2007-01-23 | 2007-09-19 | 南开大学 | Organic phosphonium transition metal salt graded hole material preparing method and the application |
| CN101402790A (en) * | 2008-11-14 | 2009-04-08 | 山东理工大学 | Sulfonation phenylphosphonic acid zirconium doping proton exchanging film and method of producing the same |
| CN101475589A (en) * | 2009-01-19 | 2009-07-08 | 南开大学 | Preparation and use of mesoporous-macroporous structure aluminum organophosphonate material |
| CN101708459A (en) * | 2009-12-03 | 2010-05-19 | 南开大学 | Method for preparing ordered mesoporous organic titanium phosphonate hybrid material and application thereof |
| CN102019203A (en) * | 2010-11-23 | 2011-04-20 | 南开大学 | Method for fast synthesizing mesoporous solid acid catalyst immobilized with sulfonic acid |
| CN102671697A (en) * | 2012-05-07 | 2012-09-19 | 天津神能科技有限公司 | Preparation method and application of mesoporous solid acid catalyst |
Non-Patent Citations (4)
| Title |
|---|
| 介孔-大孔分级孔有机膦酸锆催化合成甲基-2,3-O-异亚丙基-beta-D-呋喃核糖苷;林秀珍等;《第十六届全国分子筛大会论文集》;20111010;72页P-053部分 * |
| 分级结构介孔－大孔材料及其实际应用;刘蕾等;《石油化工》;20111231;第40卷(第3期);237-246 * |
| 疏水性固体酸催化剂应用研究进展;卢鹏等;《工业催化》;20110930;第19卷(第9期);9页3.3部分 * |
| 苯磺酸修饰的层柱磷酸锆的制备及催化应用;李颖等;《高等学校化学学报》;20110331;第32卷;731-737 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549379A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Hydrophobic solid acids and their catalytic applications in green and sustainable chemistry | |
| CN103265050B (en) | A kind of method preparing multi-stage pore zeolite molecular sieve microsphere | |
| CN102861611B (en) | Application of organic framework porous solid acid | |
| Suganuma et al. | Synthesis and acid catalysis of cellulose-derived carbon-based solid acid | |
| Guo et al. | Mesoporous H3PW12O40-silica composite: Efficient and reusable solid acid catalyst for the synthesis of diphenolic acid from levulinic acid | |
| Okamura et al. | Formation of Cu-supported mesoporous silicates and aluminosilicates and liquid-phase oxidation of benzene catalyzed by the Cu-mesoporous silicates and aluminosilicates | |
| Liu et al. | Design and synthesis of hydrophobic and stable mesoporous polymeric solid acid with ultra strong acid strength and excellent catalytic activities for biomass transformation | |
| Han et al. | Efficient confinement of ionic liquids in MIL-100 (Fe) frameworks by the “impregnation-reaction-encapsulation” strategy for biodiesel production | |
| Zhang et al. | Core–shell Pd/ZSM-5@ ZIF-8 membrane micro-reactors with size selectivity properties for alkene hydrogenation | |
| Yuan et al. | Transesterification of dimethyl oxalate with phenol over nitrogen-doped nanoporous carbon materials | |
| Lopez et al. | Mesostructured CMK-3 carbon supported Ni–ZrO2 as catalysts for the hydrodeoxygenation of guaiacol | |
| CN102633279B (en) | Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof | |
| CN102923727B (en) | A kind of silicoaluminophosphamolecular molecular sieve of hierarchical porous structure and its preparation method and application | |
| CN106732778B (en) | A kind of preparation method of immobilized heteropoly acid ionic-liquid catalyst | |
| CN102078823A (en) | Carbon-based solid acid catalyst and preparation method thereof | |
| Zhang et al. | PS-SO3H@ phenylenesilica with yolk–double-shell nanostructures as efficient and stable solid acid catalysts | |
| Masteri-Farahani et al. | Wells-Dawson heteropoly acid immobilized inside the nanocages of SBA-16 with ship-in-a-bottle method: a new recoverable catalyst for the epoxidation of olefins | |
| Zang et al. | Highly stable chromium (III) terephthalate metal organic framework (MIL-101) encapsulated 12-tungstophosphoric heteropolyacid as a water-tolerant solid catalyst for hydrolysis and esterification | |
| CN103073036B (en) | Super-microporous high-specific surface area aluminium oxide material and preparation method thereof | |
| CN104944434A (en) | Hollow AFI type molecular sieve and preparation method thereof | |
| CN102921456A (en) | Heterogeneous catalyst, preparation method of heterogeneous catalyst and application of heterogeneous catalyst | |
| Gao et al. | Alkylation of O-xylene and styrene catalyzed by cross-linked poly acidic ionic liquids catalyst with novel mesoporous-macroporous structure | |
| CN102910641B (en) | Y-Beta composite molecular sieve having uniform mesopore structures and synthetic method thereof | |
| CN104549379B (en) | Sulfated zirconium phosphonate solid strong acid porous material and preparation method | |
| Li et al. | A simple co-impregnation route to load highly dispersed Fe (III) centers into the pore structure of SBA-15 and the extraordinarily high catalytic performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |