CN101181689A - Heteropolyacid catalyst using paligorskite as carrier as well as preparation and uses thereof - Google Patents
Heteropolyacid catalyst using paligorskite as carrier as well as preparation and uses thereof Download PDFInfo
- Publication number
- CN101181689A CN101181689A CNA200710018803XA CN200710018803A CN101181689A CN 101181689 A CN101181689 A CN 101181689A CN A200710018803X A CNA200710018803X A CN A200710018803XA CN 200710018803 A CN200710018803 A CN 200710018803A CN 101181689 A CN101181689 A CN 101181689A
- Authority
- CN
- China
- Prior art keywords
- palygorskite
- acid
- carrier
- catalyst
- heteropoly
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a phosphotungstom olybdate heteropolyacid catalyst which adopts paligorskite as a carrier. Preparation steps are that: the phosphotungstom olybdate heteropolyacid is loaded on acidified paligorskite, and inhomogeneous catalyst is formed, thus thermal stability of the heteropolyacid is improved, and rear specific surface of the acid activated paligorskite can be further enlarged obviously, therefore the heteropolyacid disperse more on the surface of the carrier, and activity of the heteropolyacid is improved. The phosphotungstom olybdate heteropolyacid catalyst which adopts paligorskite as the carrier is applied to tributyl citrate synthesis, esterification rate can reach more than 90 percent, and can remain more than 85 percent after being repeatedly used without any treatment.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of catalyst that is used for catalysis synthesizing citric acid tributyl plasticizer, relating in particular to a kind of is the heteropoly phosphorus molybdenum tungstic acid catalyst and the preparation technology thereof of carrier with the palygorskite, also relates to the application of this catalyst in catalysis synthesizing citric acid tributyl plasticizer simultaneously.
Background technology
Traditional plasticizer such as dibutyl phthalate, isoamyl phthalate and dioctyl ester etc. are used for packaging material for food, can bring out carcinogenic during toy etc., and ATBC (TBC) is the safe comprehensive environment-friendly type plasticizer of performance, have nontoxic, biodegradable, therefore advantages such as intermiscibility is good, plasticizing efficiency is high, cold-resistant heat-resisting, antibacterial and mouldproof, fast light, water-fast, anti-migration and difficult volatilization obtain domestic and international attention more and more widely.
There are drawbacks such as equipment is perishable, side reaction is many, spent acid exhaust emission environment when in the technology of preparation ATBC, making catalyst with the concentrated sulfuric acid.Therefore need seek better catalyst replaces sulfuric acid.The existing method of China's patent with carbon back sulfonic acid catalyzes synthesizing citric acid tributyl (patent No.: 200610024372) and the ionic liquid-catalyzed method for preparing ATBC (patent No.: 200510086546) and with the mesopore molecular sieve is the method (patent No.: 200510030100) of Preparation of Catalyst ATBC.In addition, studies show that solid super-strong acid, heteropoly acid, inorganic salts, many materials such as rare earth compound and resinae all can be used as the catalyst of esterification.Heteropoly acid particularly, the charge density of molecular surface is low, and non-localized, and the activity of proton is quite big, thereby have very strong Bronsted acidity, and pollute for a short time, toxicity and volatility are little, etching apparatus not, selectivity is high, is a kind of eco-friendly acidic catalyst therefore.But the too little (1-5m of heteropoly acid specific area
2G
-1), especially in homogeneous catalysis, be soluble in polar solvent and cause and reclaim difficulty etc., make it to become heterogeneous phase catalyst on the carrier so be necessary it is carried on.
The palygorskite silicate mineral is bigger at China's reserves, have 2: 1 type layer chain structures, it is many that design feature shows as inner duct, specific area and porosity are all higher, can use as catalyst carrier, be the ethylene rolymerization catalyst (patent No.: 200510050205) that preparing carriers goes out with Nano purified palygorskite for example; With the palygorskite is carbonyl nickel powder, the carbonyl iron dust catalyst (patent No.: 200610051811) of carrier; With palygorskite, sepiolite be carrier in mineral lattice and the surface the attached water scavengine agent (patent No.: 200510049651) of having carried ferric ion and hydroxide thereof; It with the palygorskite nickel base hydrogenation reaction catalyst (patent No.: 200510049630) of carrier nickel and rare-earth cation and metal particle in its lattice and on the area load; And be that carrier adopts the catalyst for copper base hydrogenation reaction (patent No.: 200510049629) of ion exchange reaction with relevant element implantation palygorskite lattice with the palygorskite.
Summary of the invention
The purpose of this invention is to provide a kind of is the heteropolyacid catalyst of carrier with the palygorskite;
It is the preparation method of the heteropolyacid catalyst of carrier with the palygorskite that another object of the present invention provides a kind of;
A further object of the invention promptly is the application of heteropolyacid catalyst in catalysis synthesizing citric acid tributyl plasticizer of carrier with the palygorskite.
The present invention is the heteropolyacid catalyst of carrier with the palygorskite, be with loaded by heteropoly acid on palygorskite, form heterogeneous catalyst.Heteropoly acid has kept its inherent structure.The content of heteropoly acid in catalyst is 37～44% by weight percentage.
Palygorskite of the present invention is the palygorskite of acid activation, and its acidification technique is: use the distilled water cyclic washing to pH5～6 with sour then 60～100 ℃ of following backflow acidifyings 4～8 hours the natural palygorskite of drying, suction filtration is drying to obtain.
Heteropoly acid of the present invention is a heteropoly phosphorus molybdenum tungstic acid.
The present invention is the heteropoly phosphorus molybdenum tungstic acid Preparation of catalysts method of carrier with the acid activation palygorskite, may further comprise the steps:
1. use the distilled water cyclic washing to pH5～6 with sour then 60～100 ℃ of following backflow acidifyings 4～8 hours the natural palygorskite of drying, suction filtration, drying, porphyrize is standby;
Complete for the acidifying that makes natural palygorskite, earlier the granite-wash of natural slope thread is washed, decompress filter, drying, grind to form the fine powder below 140 orders after, carry out acidifying again.
The acid that acidifying is adopted is 1.5molL
-1HCl, the w/v of natural palygorskite and HCl are 1: 5～1: 15g/mL.
Palygorskite specific area after acid activation increases, and helps the carried heteropoly acid molecule, and its acidifying structural representation is as follows:
2. with behind the heteropoly acid porphyrize, mix by 1: 0.5～1.0 weight ratio, with distilled water backflow 12～20h under 90～100 ℃, leave standstill 8～12h again, obtain suspension with the palygorskite of above-mentioned acidifying;
The adoptable heteropoly acid of the present invention is a heteropoly phosphorus molybdenum tungstic acid, and its chemical molecular formula is as follows:
H
3PW
6M
O6O
4·nH
2O
3. above-mentioned suspension is inserted evaporating water in the container for evaporation, and after 100～110 ℃ of following dryings, promptly be able to the heteropolyacid catalyst that palygorskite is a carrier.
The load principle of loaded by heteropoly acid of the present invention on palygorskite can be represented with following formula:
In order to make the heteropoly acid high degree of dispersion on palygorskite, the palygorskite of acidifying and heteropoly acid are ground to form fine powder below 140 orders.
The present invention is the heteropoly phosphorus molybdenum tungstic acid catalyst of carrier with catalyst acid activation palygorskite, be that the heteropoly acid height is carried on the palygorskite of acidifying, the heteropoly acid heat endurance is improved, specific surface can further obviously increase behind the acid activation palygorskite, heteropoly acid is disperseed more at carrier surface, improved the activity of heteropoly acid.The palygorskite of acidifying is not only the carrier of catalyst heteropoly acid, also is the part of catalyst simultaneously, and loaded by heteropoly acid makes the activity of heteropoly acid and palygorskite form synergy on the palygorskite of acidifying, has improved the catalytic efficiency of catalyst greatly.
Catalyst of the present invention, be that the heteropoly acid height is carried on the palygorskite of acidifying, form heterogeneous catalyst, overcome and be soluble in polar solvent in the homogeneous catalysis and cause the problem that reclaims difficulty: can be repeatedly used and activity is still more stable, be easy to from reaction system, separate, and can directly reuse without any processing, overcome the problem that the homogeneous catalyst active component easily runs off preferably.Because it is catalyst stability of the present invention is good, little simultaneously to equipment corrosion.
On palygorskite, production technology is simple, reliable with the heteropoly acid high degree of dispersion for Preparation of catalysts employing refluxed evaporator absorption method of the present invention, and raw material is inexpensive.
Because the good thermal stability and the activity of catalyst of the present invention can be applied it in the preparation tributyl citrate plasticizer.
The present invention is that the heteropoly phosphorus molybdenum tungstic acid catalyst of carrier is specific as follows in the application of preparation tributyl citrate plasticizer with catalyst acid activation palygorskite:
Citric acid, n-butanol, catalyst are prepared burden with 1: 1.2: 0.1～1: 1.5: 0.3 weight ratio, and under 130～150 ℃, synthetic reaction 4～6h promptly gets ATBC.
After measured, employing the present invention is that the heteropoly phosphorus molybdenum tungstic acid catalyst of carrier is applied in the synthesizing citric acid tributyl with the palygorskite, and esterification yield can reach more than 90%, is repeatedly used all without any processing to be stabilized in more than 85%.Activity of such catalysts of the present invention is good simultaneously, the catalytic efficiency height, and in the reaction of synthesizing citric acid tributyl, catalyst consumption is few, and cost is low.
The specific embodiment
Embodiment 1, the present invention are the heteropoly phosphorus molybdenum tungstic acid Preparation of catalysts of carrier with the acidifying palygorskite:
1. earlier the granite-wash of natural slope thread is washed, decompress filter, drying, grind to form fine powder below 140 orders with grinder after; Use 1.5molL
-1HCl was 60～100 ℃ of following backflow acidifyings 4～8 hours; The w/v of palygorskite and HCl is 1: 5～1: 15g/mL; Use the distilled water cyclic washing to pH5～6 then, suction filtration, drying grinds to form fine powder below 140 orders with grinder, and is standby;
2. after Keggin type heteropoly phosphorus molybdenum tungstic acid being ground to form fine powder below 140 orders with grinder, mix by 1: 0.5～1.0 weight ratio with the palygorskite of above-mentioned acidifying, with distilled water backflow 12～20h under 90～100 ℃, rotating speed is 300r/min again, leave standstill 8～12h, obtain suspension;
3. above-mentioned suspension is inserted in the container for evaporation, stir in 85 ℃ of water-baths, rotating speed is 120r/min, directly with the moisture evaporate to dryness, and in 105 ℃ of constant pressure and dry 4h; Promptly get catalyst of the present invention.
Embodiment 2, be the technology of the heteropoly phosphorus molybdenum tungstic acid catalyst synthesizing citric acid tributyl of carrier with the acidifying palygorskite:
Citric acid, n-butanol, catalyst are prepared burden with 1: 1.2: 0.1 weight ratio, and under 130 ℃, synthetic reaction 6h promptly gets ATBC.Measure esterification yield: 81.2%.
Embodiment 3, be the technology of the heteropoly phosphorus molybdenum tungstic acid catalyst synthesizing citric acid tributyl of carrier: with citric acid, n-butanol, catalyst weight ratio batching with 1: 1.4: 0.2 with the acidifying palygorskite, under 145 ℃, synthetic reaction 5h promptly gets ATBC.Measure esterification yield: 90.2%.
Embodiment 4, be the technology of the heteropoly phosphorus molybdenum tungstic acid catalyst synthesizing citric acid tributyl of carrier: with citric acid, n-butanol, catalyst weight ratio batching with 1: 1.5: 0.3 with the acidifying palygorskite, under 130 ℃, synthetic reaction 5h promptly gets ATBC.Measure esterification yield: 83.5%.
Claims (10)
1. one kind is the heteropoly phosphorus molybdenum tungstic acid catalyst of carrier with the palygorskite, it is characterized in that: be with loaded by heteropoly acid on palygorskite, form heterogeneous catalyst; The content of described heteropoly acid in catalyst is 37～44% by weight percentage.
2. be the heteropoly phosphorus molybdenum tungstic acid catalyst of carrier according to claim 1 with the palygorskite, it is characterized in that: described palygorskite is the palygorskite of acid activation, its acidification technique is: use acid 60～100 ℃ of following backflow acidifyings 4～8 hours the natural palygorskite of drying, use the distilled water cyclic washing to pH5～6 then, suction filtration, dry and get; The acid of being adopted is 1.5molL
-1HCl, the w/v of natural palygorskite and HCl are 1: 5～1: 15g/mL.
3. be the heteropoly phosphorus molybdenum tungstic acid catalyst of carrier with the palygorskite according to claim 1, it is characterized in that: described heteropoly acid is a heteropoly phosphorus molybdenum tungstic acid.
4. be the preparation method of the heteropolyacid catalyst of carrier with the palygorskite according to claim 1, may further comprise the steps:
1. use acid 60～100 ℃ of following backflow acidifyings 4～8 hours the natural palygorskite of drying, use the distilled water cyclic washing to pH value 5～6, suction filtration, drying, porphyrize is standby;
2. with behind the heteropoly acid porphyrize, mix by 1: 0.5～1.0 weight ratio, with distilled water backflow 12～20h under 90～100 ℃, leave standstill 8～12h again, obtain suspension with the palygorskite of above-mentioned acidifying;
3. above-mentioned suspension is inserted evaporating water in the container for evaporation, being drying to obtain with the palygorskite is the heteropolyacid catalyst of carrier.
5. as being the preparation method of the heteropolyacid catalyst of carrier as described in the claim 4, it is characterized in that with the palygorskite: step 1. be earlier the granite-wash of natural slope thread is washed, decompress filter, drying, grind to form the fine powder below 140 orders after, carry out acidifying again.
6. as being the preparation method of the heteropolyacid catalyst of carrier with the palygorskite as described in the claim 4, it is characterized in that: the acid that 1. step is adopted is 1.5molL
-1HCl, the w/v of natural palygorskite and HCl are 1: 5～1: 15g/mL.
7. as being the preparation method of the heteropolyacid catalyst of carrier with the palygorskite as described in the claim 4, it is characterized in that: the heteropoly acid of step in 2. grinds to form the following fine powder of 140 orders.
8. as being the preparation method of the heteropolyacid catalyst of carrier with the palygorskite as described in the claim 4, it is characterized in that: the heteropoly acid of step in 2. is heteropoly phosphorus molybdenum tungstic acid.
9. as being the preparation method of the heteropolyacid catalyst of carrier with the palygorskite as described in the claim 4, it is characterized in that: the 3. described drying of step is in 100～110 ℃ of following constant pressure and dries.
10. wanting as described in 1 with the palygorskite as right is the application of heteropolyacid catalyst in the preparation ATBC of carrier, be that citric acid, n-butanol, catalyst are prepared burden with 1: 1.2: 0.1～1: 1.5: 0.3 weight ratio, under 130～150 ℃, synthetic reaction 4～6h promptly gets ATBC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710018803A CN101181689B (en) | 2007-09-13 | 2007-09-13 | Heteropolyacid catalyst using paligorskite as carrier as well as preparation and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710018803A CN101181689B (en) | 2007-09-13 | 2007-09-13 | Heteropolyacid catalyst using paligorskite as carrier as well as preparation and uses thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101181689A true CN101181689A (en) | 2008-05-21 |
| CN101181689B CN101181689B (en) | 2010-05-19 |
Family
ID=39447194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710018803A Expired - Fee Related CN101181689B (en) | 2007-09-13 | 2007-09-13 | Heteropolyacid catalyst using paligorskite as carrier as well as preparation and uses thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101181689B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916864A (en) * | 2010-08-13 | 2010-12-15 | 西北师范大学 | Palygorskite/carbon composite material, and preparation and application thereof |
| CN102249916A (en) * | 2011-05-26 | 2011-11-23 | 南京化工职业技术学院 | Continuous production process for tributyl citrate |
| CN105251538A (en) * | 2015-10-28 | 2016-01-20 | 湖北师范学院 | Preparation method of catalyst H6P2W15Mo3O62/TiO2 and n-pentyl acetate |
| CN106582814A (en) * | 2016-12-20 | 2017-04-26 | 福州大学 | Epoxide ring-opening reaction catalyst and preparation method thereof |
| CN109569579A (en) * | 2018-12-26 | 2019-04-05 | 淮南安信泰科技有限公司 | A kind of method of the immobilized tungsten oxide preparation tributyl citrate of attapulgite clay |
-
2007
- 2007-09-13 CN CN200710018803A patent/CN101181689B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916864A (en) * | 2010-08-13 | 2010-12-15 | 西北师范大学 | Palygorskite/carbon composite material, and preparation and application thereof |
| CN102249916A (en) * | 2011-05-26 | 2011-11-23 | 南京化工职业技术学院 | Continuous production process for tributyl citrate |
| CN102249916B (en) * | 2011-05-26 | 2014-07-23 | 南京化工职业技术学院 | Continuous production process for tributyl citrate |
| CN105251538A (en) * | 2015-10-28 | 2016-01-20 | 湖北师范学院 | Preparation method of catalyst H6P2W15Mo3O62/TiO2 and n-pentyl acetate |
| CN106582814A (en) * | 2016-12-20 | 2017-04-26 | 福州大学 | Epoxide ring-opening reaction catalyst and preparation method thereof |
| CN106582814B (en) * | 2016-12-20 | 2019-02-22 | 福州大学 | A kind of epoxy ring opening reaction catalyst and preparation method thereof |
| CN109569579A (en) * | 2018-12-26 | 2019-04-05 | 淮南安信泰科技有限公司 | A kind of method of the immobilized tungsten oxide preparation tributyl citrate of attapulgite clay |
| CN109569579B (en) * | 2018-12-26 | 2021-10-08 | 淮南安信泰科技有限公司 | Method for preparing tributyl citrate from attapulgite clay immobilized tungsten oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101181689B (en) | 2010-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101181689B (en) | Heteropolyacid catalyst using paligorskite as carrier as well as preparation and uses thereof | |
| Zhou et al. | Recent advances in polyoxometalate-based heterogeneous catalytic materials for liquid-phase organic transformations | |
| Wang et al. | Graphene-supported Au–Pd bimetallic nanoparticles with excellent catalytic performance in selective oxidation of methanol to methyl formate | |
| CN102352003B (en) | Preparation method of phenolic resin microballoons and method for preparing phenolic resin-based carbon spheres by use of preparation method | |
| JP4041512B2 (en) | Glycerol dehydration catalyst, glycerin dehydration catalyst production method, acrolein production method, and acrolein derivative production method | |
| CN104248991A (en) | Spherical montmorillonite mesoporous composite carrier, supported catalyst, preparation methods of spherical montmorillonite mesoporous composite carrier and supported catalyst, use of supported catalyst and preparation method of ethyl acetate | |
| Zhang et al. | Construction of a Keggin heteropolyacid/Ni-MOF catalyst for esterification of fatty acids | |
| CN102781580A (en) | Process for preparing catalyst used in production of unsaturated aldehyde and/or unsaturated carboxylic acid by dehydration reaction of glycerin, and catalyst obtained | |
| CN104248980A (en) | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method | |
| Li et al. | Selective aerobic oxidation of glycerol over zirconium phosphate-supported vanadium catalyst | |
| CN113509929A (en) | Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof | |
| CN103084213B (en) | Catalyst for synthesizing 2,6-xylenol as well as preparation method of catalyst and method for synthesizing 2,6-xylenol | |
| CN106268806A (en) | The catalyst of a kind of methanol carbonyl and preparation thereof and application | |
| CN101966455B (en) | Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process | |
| WO2020192477A1 (en) | Catalyst and method for preparing isopentyl diol | |
| Behera et al. | Fascinating and challenging role of tungstate promoted vanadium phosphate towards solvent free esterification of oleic acid | |
| CN109908926A (en) | A kind of preparation method of ozone catalytic oxidation catalyst | |
| Feng et al. | One-step solvent-free aerobic oxidation of aliphatic alcohols to esters using a tandem Sc–Ru⊂ MOF catalyst | |
| CN103157472B (en) | Preparation method for supported catalyst used for preparing cyclopentanol through furfural liquid phase hydrogenation | |
| Ghiaci et al. | Oxidation of cyclohexanol to adipic acid with molecular oxygen catalyzed by ZnO nanoparticles immobilized on hydroxyapatite | |
| CN105727954B (en) | A kind of preparation method of synthesis gas preparing natural gas catalyst | |
| CN114602512B (en) | Preparation method of esterification catalyst | |
| CN106944139A (en) | A kind of heteropoly acid ammonium salt catalyst and preparation method thereof | |
| CN105749939B (en) | A kind of montmorillonite-loaded tungsten oxide catalyst of phosphoric acid modification, preparation method and application | |
| CN107876040B (en) | Catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100519 Termination date: 20120913 |