CN101797520B - Aluminum doped organic/inorganic hybrid clay catalyst, and preparation method and application thereof - Google Patents
Aluminum doped organic/inorganic hybrid clay catalyst, and preparation method and application thereof Download PDFInfo
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- CN101797520B CN101797520B CN2010101300240A CN201010130024A CN101797520B CN 101797520 B CN101797520 B CN 101797520B CN 2010101300240 A CN2010101300240 A CN 2010101300240A CN 201010130024 A CN201010130024 A CN 201010130024A CN 101797520 B CN101797520 B CN 101797520B
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Abstract
The invention relates to a solid acid catalyst, in particular to an aluminum doped organic/inorganic hybrid clay catalyst, which is characterized in that: the specific surface area is 10-250m <2>/g, and the pore volume is 0.2-0.8 cm<3>/g; the aluminum doped organic/inorganic hybrid clay catalyst comprises 8 to 45 percent of alumina, 40 to 80 percent of monox, and 0.5 to 10 percent of organic modifier, wherein the organic modifier is alkyl siloxane containing sulfonic acid groups, an alkyl siloxane containing sulfhydryl groups, or a mixture thereof. The catalyst is prepared by introducing sulfonic acidic organic functional groups to combine aluminum doped modified clay. The catalyst has the advantages of easy acidity adjustment, high activity, high strength and good stability, and can be used for catalyzing tetrahydrofuran polymerization.
Description
Technical field
The present invention relates to solid acid catalyst, be specifically related to a kind of aluminium doping hybrid inorganic-organic clay catalyst and preparation method thereof, with and application in tetrahydrofuran polyreaction.
Background technology
PolyTHF (PTHF), be to make straight-chain polyether dihydroxylic alcohols macromolecular compound by tetrahydrofuran ring opening polymerization, claim that again (polytetramethylene ether glycol PTMEG), poly-tetramethylene ether diol, also claims polytetramethylene ether to polytetramethylene ether diol.Structural formula is HO-(CH
2CH
2CH
2CH
2O-)
n-H, its main application is to produce Spandex fiber (China is called spandex) and polyurethane elastomer.The PolyTHF industrial products have different sizes such as relative molecular mass 600,1000,1500,1800,2000,3000, and the average molecular mass that is used to produce the PolyTHF of spandex is 1800,2000, accounts for more than 60% of total flow.
Make a general survey of document, patent report, tetrahydrofuran polyreaction is to realize down through the cation catalytic condition.The H.Meerwein reported first was utilized [EtO in 1936
3] BF
4The catalysis tetrahydrofuran ring opening polymerization; Subsequently, all kinds polymerization catalyst continues to bring out.As: mineral acids such as oleum, perchloric acid may be used on the oxolane catalytic polymerization.
Patents [ZL 98125036.X] such as Asahi Kasei Corporation's patent [ZL 99800941.5], Huajin Chemical's patent [ZL02132519.7], the Zhang Hongzhi of Peking University, international (Suzhou Industrial Park) new material research and development Co., Ltd's patents of middleization [ZL 02123481.7] report are applied to tetrahydrofuran polyreaction with heteropoly acid as catalyst.
BASF AG's patent [ZL 98805481.7, ZL 98812121.2,, ZL 99801684.5, ZL 03823035.6, ZL200380107359.9] has reported that the clay of handling the specific place of production, composition, structure with concentrated acid is used for the preparation of catalyzing tetrahydrofuran polymerization agent; These methods adopt concentrated acid to handle the equipment that clay needs anti-strong acid corrosion, and production process can produce a large amount of acidic wastes.
Summary of the invention
The object of the present invention is to provide a kind of aluminium doping hybrid inorganic-organic clay catalyst and preparation method thereof, method for preparing catalyst is simple, reaction condition is gentle, the raw clay grade requirement is low, the source is wider, utilization rate is high, environmental pollution is little, suitability for industrialized production, and catalyst can be used for tetrahydrofuran polyreaction.
A kind of aluminium doping hybrid inorganic-organic clay catalyst provided by the invention, its specific area 10-250m
2/ g, pore volume 0.2-0.8cm
3/ g contains: aluminium oxide 8-45%, silica 40-80%, organic modifiers 0.5-10%;
Described organic modifiers is to contain sulfonic alkyl siloxanes, or contain the alkyl siloxanes of sulfydryl, or their mixture, describedly contain sulfonic alkyl siloxanes, as: sulfonic group cyclopentadiene ethyl triethoxysilane, sulfonic group cyclopentadiene ethyl trimethoxy silane, sulfonic acid ethyl trimethoxy silane, sulfonic benzo trimethoxy silane etc.; The described alkyl siloxanes that contains sulfydryl, as: sulfydryl cyclopentadiene ethyl triethoxysilane, sulfydryl cyclopentadiene ethyl trimethoxy silane, mercaptopropyl trimethoxysilane, mercapto ethyl trimethoxy silane etc.
The preparation method of a kind of aluminium doping hybrid inorganic-organic clay catalyst provided by the invention comprises the steps:
1) clay is added in the mineral acid solution that concentration is 0.2-6M, the clay addition is the 8-50% of mineral acid solution volume, and room temperature condition stirs 2-5h, separation, 100-150 ℃ dry 5-24h then down;
2) step 1) being handled the clay that obtains adds in the organic media, the clay addition is the 9-60% of organic media volume, add the organic modifiers that contains sulfonic alkyl siloxanes again, the control addition is the 1-25% of clay quality, 30 ℃ are reacted 2-24h to organic media reflux temperature condition, then add aluminum feedstock, make that alumina amount is the 2-40% of siliconoxide mass in the clay, continue isothermal reaction 1-12h, separate, 30-120 ℃ of drying is under nitrogen atmosphere, in 150-200 ℃ of activation 2-10h, obtain catalyst.
The preparation method of another kind of aluminium doping hybrid inorganic-organic clay catalyst comprises the steps:
1) clay is added in the mineral acid solution that concentration is 0.2-6M, the clay addition is the 8-50% of mineral acid solution volume, and room temperature condition stirs 2-5h, separation, 100-150 ℃ dry 5-24h then down;
2) step 1) being handled the clay that obtains adds in the organic media, the clay addition is the 9-60% of organic media volume, the organic modifiers that adds the alkyl siloxanes that contains sulfydryl again, the control addition is the 1-25% of clay quality, 30 ℃ are reacted 2-24h to organic media reflux temperature condition, the hydrogen peroxide that adds organic media 10-30%, isothermal reaction 2-48h then adds aluminum feedstock, makes that alumina amount is the 2-40% of siliconoxide mass in the clay, continue isothermal reaction 1-12h, separate, 30-120 ℃ of drying is under nitrogen atmosphere, in 150-200 ℃ of activation 2-10h, obtain catalyst.
Clay described in above-mentioned two kinds of preparation methods is kaolin, imvite, bentonite or attapulgite, or contains the mixed clay of their compositions, and the content requirement of clay is at 30-98%.
Described mineral acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.
Described organic media is acetonitrile, toluene, dimethylbenzene, N, dinethylformamide etc.
Described aluminum feedstock can be aluminium isopropoxide, butyl aluminium or silicon-aluminium composite oxide powder.
The application of aluminium doping hybrid inorganic-organic clay catalyst in catalyzing tetrahydrofuran polymerization: take by weighing above-mentioned catalyst and add in the Industrial Grade Tetrahydrofuran polymer raw (containing 10% acetic anhydride), it is 1-95% that the control catalytic amount accounts for the tetrahydrofuran by polymerization volume feed, under 30-55 ℃ of temperature conditions, reaction 1-72h, isolating polymer calculates the polymerization yield, in the 30%-70% scope, measure relative molecular weight, in the 1450-2050 scope, molecular weight distribution is at 1.5-2.3.
Polymer yield adopts formula Y=m
2/ m
1* 100% calculates, and Y refers to reactive polymeric thing yield, m
1The mixed material amount of pipetting: m behind the finger reaction certain hour
2The amount of finger residue after volatile materials is removed in distillation; Polymerizate number average relative molecular weight (Mn) is measured and is determined the product hydroxyl value with reference to the GB12008.3-89 method, calculates according to Mn=2000 * 56.105/ hydroxyl value then.
The advantage and the effect that have of the present invention compared with prior art: in the preparation process of the present invention, the selected clay place of production, compositing range are more extensive, need not the elite mineral of high-grade; Adopt the organic functional group method of modifying, can regulate the Bronsted acid intensity and the acid amount of clay matrix; An amount of adulterated al species can be adjusted the acid matter of polymerization catalyst, more help preparing the catalyst material that is applicable to the synthetic about 1800-2000 polymer of relative molecular weight of catalysis; Preparation of catalysts process of the present invention, the concentrated acid that does not have aforementioned publication to report is handled the process of clay, and acid material, organic media fully can be recycling, help reducing pollution, reduction equipment, production cost, increase clay resource utilization rate.In a word, the invention provides the mix preparation method of organic hybrid clay solid acid catalyst of the aluminium that a kind ofly has inorganic material intensity height, good stability and organic material softness concurrently, can modify dual characteristics.This legal system is equipped with mild condition, easy operating, polymerization catalyst regulating measure (modification of organic acid functional group, aluminium mix) flexibly, is the effective way of a kind of raising than low grade natural clay utilization rate, therefore has application prospect.
The specific embodiment
Embodiment 1
Weighing 50g natural montmorillonite adds 2M hydrochloric acid solution 150ml, stirring at room 3h, separation, 120 ℃ of dry 10h change in the 180ml toluene liquid then, add mercaptopropyl trimethoxysilane 5g, 95 ℃ of temperature conditions react 12h down, then add the 5g aluminium isopropoxide, continue isothermal reaction 8h, add toluene wash 24h, change over to subsequently in the solution that 100g is made into by hydrogen peroxide, water and methyl alcohol (volume ratio is 1.5: 3: 20), 40 ℃ are stirred 12h, separate, through 180mL 0.25mol.dm
-3H
2SO
4Solution room temperature stir process 12h separates, and 80 ℃ of dryings under nitrogen atmosphere, in 180 ℃ of activation 6h, obtain white polymerization catalyzed agent material.
Embodiment 2
Weighing 50g natural kaolin adds 4M hydrochloric acid solution 150ml, stirring at room 5h, separation, 120 ℃ of dry 10h change in the 180ml toluene liquid then, add mercaptopropyl trimethoxysilane 8g, counterflow condition is reaction 10h down, then add the 5g aluminium isopropoxide, continue isothermal reaction 8h, add toluene wash 24h, change over to subsequently in the solution that 120g is made into by hydrogen peroxide, water and methyl alcohol (volume ratio is 1.5: 3: 20), 40 ℃ are stirred 12h, separate, through 180mL 0.25moldm
-3H
2SO
4Solution room temperature stir process 12h separates, and 80 ℃ of dryings under nitrogen atmosphere, in 200 ℃ of activation 6h, obtain white polymerization catalyzed agent material.
Embodiment 3
Measure 65ml Industrial Grade Tetrahydrofuran polymer material (containing 10% acetic anhydride), add the foregoing description 2 polymerization catalyst 4g, at 40 ℃ of reactions 10 hours, separation, yield 57%, number-average molecular weight 1728, molecular weight distribution 2.1.
Embodiment 4
Weighing 50g natural montmorillonite adds 0.5M hydrochloric acid solution 150ml, stirring at room 3h, separation, 120 ℃ of dry 10h change in the 160ml dimethylbenzene liquid then, add sulfonic group cyclopentadiene ethyl trimethoxy silane 8g, counterflow condition is reaction 10h down, then adds the 6g aluminium isopropoxide, continues isothermal reaction 8h, add toluene wash 24h, separate, 80 ℃ of dryings are under nitrogen atmosphere, in 200 ℃ of activation 6h, obtain white polymerization catalyzed agent material.
Embodiment 5
Weighing 50g natural kaolin adds 4M hydrochloric acid solution 150ml, stirring at room 5h, separation, 120 ℃ of dry 10h change in the 180ml toluene liquid then, add sulfydryl cyclopentadiene ethyl trimethoxy silane 8g, counterflow condition is reaction 10h down, then add the 5g aluminium isopropoxide, continue isothermal reaction 8h, add toluene wash 24h, change over to subsequently in the solution that 120g is made into by hydrogen peroxide, water and methyl alcohol (volume ratio is 1.5: 3: 20), 40 ℃ are stirred 12h, separate, through 180mL 0.25mol.dm
-3H
2SO
4Solution room temperature stir process 12h separates, and 80 ℃ of dryings under nitrogen atmosphere, in 180 ℃ of activation 6h, obtain white polymerization catalyzed agent material.
Embodiment 6
Weighing 50g natural kaolin, add 4M hydrochloric acid solution 150ml, stirring at room 5h, separation, 120 ℃ of dry 10h, change over to then in the 180ml toluene liquid, add sulfydryl cyclopentadiene ethyl trimethoxy silane 5g, sulfonic group cyclopentadiene ethyl trimethoxy silane 2.2g, counterflow condition is reaction 10h down, then add 5g silicon-aluminium composite oxide powder, continue isothermal reaction 8h, add toluene wash 24h, change over to subsequently in the solution that 120g is made into by hydrogen peroxide, water and methyl alcohol (volume ratio is 1.5: 3: 20), 40 ℃ are stirred 12h, separate, through 180mL 0.25mol.dm
-3H
2SO
4Solution room temperature stir process 12h separates, and 80 ℃ of dryings under nitrogen atmosphere, in 180 ℃ of activation 6h, obtain white polymerization catalyzed agent material.
Embodiment 7
Measure 65ml Industrial Grade Tetrahydrofuran polymer material, add the foregoing description 4 polymerization catalyst 4g, at 40 ℃ of reactions 10 hours, separation, yield 59%, number-average molecular weight 1752, molecular weight distribution 1.9.
Embodiment 8
Measure 65ml Industrial Grade Tetrahydrofuran polymer material, add the foregoing description 6 polymerization catalyst 4g, at 38 ℃ of reactions 8 hours, separation, yield 66%, number-average molecular weight 1852, molecular weight distribution 1.85.
Claims (10)
1. an aluminium doping hybrid inorganic-organic clay catalyst is characterised in that its specific area 10-250m
2/ g, pore volume 0.2-0.8cm
3/ g contains: aluminium oxide 8-45%, silica 40-80%, organic modifiers 0.5-10%; Described organic modifiers is to contain sulfonic alkyl siloxanes, or contains the alkyl siloxanes of sulfydryl, or their mixture.
2. aluminium doping hybrid inorganic-organic clay catalyst as claimed in claim 1, it is characterized in that described to contain sulfonic alkyl siloxanes be sulfonic group cyclopentadiene ethyl triethoxysilane, sulfonic group cyclopentadiene ethyl trimethoxy silane, sulfonic acid ethyl trimethoxy silane or sulfonic benzo trimethoxy silane.
3. aluminium doping hybrid inorganic-organic clay catalyst as claimed in claim 1, it is characterized in that the described alkyl siloxanes that contains sulfydryl is sulfydryl cyclopentadiene ethyl triethoxysilane, sulfydryl cyclopentadiene ethyl trimethoxy silane, mercaptopropyl trimethoxysilane or mercapto ethyl trimethoxy silane.
4. the preparation method of aluminium doping hybrid inorganic-organic clay catalyst as claimed in claim 1 is characterized in that, comprises the steps:
1) clay is added in the mineral acid solution that concentration is 0.2-6M, the clay addition is the 8-50% of mineral acid solution volume, and room temperature condition stirs 2-5h, separation, 100-150 ℃ dry 5-24h then down;
2) step 1) being handled the clay that obtains adds in the organic media, the clay addition is the 9-60% of organic media volume, add the organic modifiers that contains sulfonic alkyl siloxanes again, the control addition is the 1-25% of clay quality, 30 ℃ are reacted 2-24h to organic media reflux temperature condition, then add aluminum feedstock, make that alumina amount is the 2-40% of siliconoxide mass in the clay, continue isothermal reaction 1-12h, separate, 30-120 ℃ of drying is under nitrogen atmosphere, in 150-200 ℃ of activation 2-10h, obtain catalyst.
5. the preparation method of aluminium doping hybrid inorganic-organic clay catalyst as claimed in claim 1 is characterized in that, comprises the steps:
1) clay is added in the mineral acid solution that concentration is 0.2-6M, the clay addition is the 8-50% of mineral acid solution volume, and room temperature condition stirs 2-5h, separation, 100-150 ℃ dry 5-24h then down;
2) step 1) being handled the clay that obtains adds in the organic media, the clay addition is the 9-60% of organic media volume, the organic modifiers that adds the alkyl siloxanes that contains sulfydryl again, the control addition is the 1-25% of clay quality, 30 ℃ are reacted 2-24h to organic media reflux temperature condition, the hydrogen peroxide that adds organic media 10-30%, isothermal reaction 2-48h then adds aluminum feedstock, makes that alumina amount is the 2-40% of siliconoxide mass in the clay, continue isothermal reaction 1-12h, separate, 30-120 ℃ of drying is under nitrogen atmosphere, in 150-200 ℃ of activation 2-10h, obtain catalyst.
6. as the preparation method of claim 4 or 5 described aluminium doping hybrid inorganic-organic clay catalysts, it is characterized in that described clay is kaolin, imvite, bentonite or attapulgite, or contain the mixed clay of their compositions.
7. as the preparation method of claim 4 or 5 described aluminium doping hybrid inorganic-organic clay catalysts, it is characterized in that described mineral acid is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.
8. as the preparation method of claim 4 or 5 described aluminium doping hybrid inorganic-organic clay catalysts, it is characterized in that described organic media is acetonitrile, toluene, dimethylbenzene or N, dinethylformamide.
9. as the preparation method of claim 4 or 5 described aluminium doping hybrid inorganic-organic clay catalysts, it is characterized in that described aluminum feedstock is aluminium isopropoxide, butyl aluminium or silicon-aluminium composite oxide powder.
10. the application of aluminium doping hybrid inorganic-organic clay catalyst as claimed in claim 1 in catalyzing tetrahydrofuran polymerization.
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| CN103657684B (en) * | 2013-11-22 | 2015-10-28 | 江苏大学 | The preparation method of the acid composite catalyst of a kind of halloysite nanotubes-sulfonic group-Cr (III) ion |
| CN104923307A (en) * | 2015-05-13 | 2015-09-23 | 安徽金邦医药化工有限公司 | Low-energy consumption non-corrosive compound solid acid catalyst and preparation method therefor |
| CN105460942A (en) * | 2015-10-21 | 2016-04-06 | 北京化工大学 | Preparation of modified sodium-based bentonite for solidifying mercury in soil |
| CN111167524B (en) * | 2020-03-09 | 2021-11-23 | 农业农村部环境保护科研监测所 | Porous acid-base bifunctional solid catalyst, and preparation method and application thereof |
Citations (4)
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| CN1340485A (en) * | 2000-08-29 | 2002-03-20 | 中国石油化工集团公司 | Process for preparing selective disproportionation catalyst of toluene |
| CN1590413A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Silicon modified aluminium oxide and preparation, and its use in loading metallocene catalyst |
| CN1765499A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Preparation method of toluene selective disproportionation catalyst |
| CN101230210A (en) * | 2007-12-28 | 2008-07-30 | 河北工业大学 | Method for preparing organic modified silicate mineral clay |
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| JP2741233B2 (en) * | 1989-02-13 | 1998-04-15 | チッソ株式会社 | Solid acid catalyst and method of using the same |
| WO2000045951A1 (en) * | 1999-02-05 | 2000-08-10 | Waters Investments Limited | Porous inorganic/organic hybrid particles for chromatographic separations and process for its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340485A (en) * | 2000-08-29 | 2002-03-20 | 中国石油化工集团公司 | Process for preparing selective disproportionation catalyst of toluene |
| CN1590413A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Silicon modified aluminium oxide and preparation, and its use in loading metallocene catalyst |
| CN1765499A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Preparation method of toluene selective disproportionation catalyst |
| CN101230210A (en) * | 2007-12-28 | 2008-07-30 | 河北工业大学 | Method for preparing organic modified silicate mineral clay |
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