CN1150995C - Microporous material carried metal complex-ionic liquid catalyst - Google Patents
Microporous material carried metal complex-ionic liquid catalystInfo
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- CN1150995C CN1150995C CNB021195684A CN02119568A CN1150995C CN 1150995 C CN1150995 C CN 1150995C CN B021195684 A CNB021195684 A CN B021195684A CN 02119568 A CN02119568 A CN 02119568A CN 1150995 C CN1150995 C CN 1150995C
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- palladium
- ionic liquid
- catalyst
- catalyzer
- complex
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Abstract
The present invention relates to a microporous material carried metal complex, namely an ionic liquid catalyst which loads 1, 3-dialkyl imidazole, alkyl pyridine ionic liquid and palladium complexes in micropore titanium-silicone compound oxide by the sol-gel process of titanate and silicate. The catalyst can catalyze the oxonation of nitrogen-containing compounds to prepare carbamate and disubstituted urea at 80 DEG C to 200 DEG C under the conditions that the pressure ratio of oxygen to carbon monoxide is from 0:1 to 1:2, and the total pressure ratio is from 1.0 to 7.0MPas. The catalyst is characterized in that the catalytic activity is high; the ionic liquid and the palladium complexes are loaded or bounded in carriers; active components are difficultly lost; simultaneously, the catalyst is capable of being repeatedly used, reduces the dosage of the ionic liquid and the palladium complexes, effectively reduces the cost and has good industrial application prospects.
Description
Technical field
The present invention relates to a kind of microporous material carried metal complex-ionic liquid catalyst, this catalyzer is catalysis nitrogenous compound oxidative carbonylation system carbamate and 2-substituted carbamide efficiently.
Background technology
Noble metal catalyst all has important status in every field such as research and productions, its excellent catalytic performance has obtained extensive studies and application, palladium, ruthenium, the composition catalyst system of rhodium etc. has very high activity and selectivity in homogeneous catalytic reaction.But because these precious metals complex catalyst systems mainly use with the homogeneous form, although can obtain very high transformation efficiency and selectivity, its catalyzer and reaction system, product separation reclaim, and problems such as repeated use are difficult to solve for a long time.Simultaneously, in order to dissolve such catalyzer and for it provides suitable reaction environment, must to use volatile in a large number, deleterious organic solvent, this just easily causes serious contaminate environment.How to realize the heterogenize of homogeneous phase noble metal catalyst, promote its application and develop into the important content of this area research.But heterogenize process in the past is difficult to keep the homogeneity of original reaction environment of homogeneous catalyst and catalytic active center, often causes problems such as active decline, selectivity reduction.Therefore, when keeping homogeneous catalysis system high reactivity, highly selective characteristics, develop easily separated, reusable, can keep homogeneous catalyst characteristic and eco-friendly precious metals complex catalyst system not only to have important practical value but also have good society and environmental benefit.
Meanwhile, by nitrogen-containing heterocycle compound halogenated alkyl pyridine, halogenation 1, the ionic liquid that is in a liquid state under the room temperature that 3-dialkylimidazolium and non-metallic halide constitute are receiving the acceptance and the concern of countries in the world catalysis circle and petroleum chemical enterprise circle as " cleaning " solvent and new catalyst system.The normal temperature ionic liquid has excellent chemistry and thermostability, and steam forces down, and can work under comparatively high temps, utilizes methods such as extraction, distillation ionic liquid can be separated with product, reaches the purpose of recycling.The eighties, early stage Britain BP company and French research institutions such as IFP began to explore the possibility of ionic liquid as solvent and catalyzer.Concrete research mainly concentrates on ionic liquid-catalyzed system and replaces traditional sulfuric acid, hydrofluoric acid and Lewis acid catalyzed reaction process, and obtain goodish result, react as Friedel-Crafts, alkylation, isomerization, dimerizing olefins and shortening, Diels-Alder reaction and the (T.Welton such as extracting and separating system that constitute with supercritical co, Chem.Rev., 1999,99,2071; L.A.blanchard et al, Nature, 1999,399,6731).Research shows that also metal complex catalyst combines with ionic liquid can form common synergistic effect, can further improve catalyst activity and selects then property, improves catalyst stability.But because the ionic liquid price is relatively costly, consumption is relatively large and limited its widespread use.Therefore when the research ionic liquid is used, how reducing ion liquid consumption and improving its service efficiency also becomes ionic liquid needed the problem that solves before entering practical application.If metallo-organic complex is combined with ionic liquid, utilize characteristics such as ion liquid high boiling point, low-steam pressure, realize that homogeneous catalysis system " high dispersive " that a kind of metal complex and ionic liquid constitutes is loaded into the preparation process in the poromerics, again have catalyst-loaded active ingredient high dispersing with selecting then in the property in the activity that keeps the metal complex-ionic liquid system, consumption is few, the easy and isolating advantage of product.This just when keeping the homogeneous catalysis characteristics, has reduced ion liquid consumption realizing the homogeneous catalyst heterogenize again, form a kind of with in the past the different catalyst system of " homogeneous catalysis heterogenize " catalyzer.
Summary of the invention
The object of the present invention is to provide a kind of microporous material carried metal complex-ionic liquid catalyst.
Direct purpose of the present invention is to provide a micropore titanium silicon composite oxides loaded palladium complex compound-ionic-liquid catalyst, and this catalyzer is catalysis nitrogenous compound oxidative carbonylation system carbamate and 2-substituted carbamide reaction efficiently.
Catalyzer of the present invention, it is characterized in that metallo-organic complex and ionic liquid are by in the hole that is loaded into poromerics of high dispersive, form a kind of microcosmic homogeneous phase, macroscopical heterogenetic catalyst system, wherein used poromerics is a Ti-Si composite oxide, used metallo-organic complex is a palladium complex, used ionic liquid is 1,3-dialkylimidazolium or Fixanol.
Catalyzer of the present invention, the loading that it is characterized in that palladium are 0.04% to 3% of titanium-silicon composite oxide carrier weight, and ion liquid loading is 1% to 15% of a vehicle weight, titanium in the Ti-Si composite oxide, and the mol ratio of silicon is for being 1: 50 to 1: 1.
Catalyzer of the present invention is characterized in that 1, and the substituted alkyl chain length of 3-dialkylimidazolium or Fixanol is C
1To C
8Alkyl chain, the anionicsite of salt is a fluorine, chlorine, bromine, iodine, fluoroboric acid root, hexafluorophosphoric acid root, sulfate radical, nitrate radical, trifluoracetic acid root, trifluoromethanesulfonic acid root.
Preparation of catalysts method of the present invention is characterized in that this method may further comprise the steps:
A) palladium complex dissolves or is complexed to 1, in 3-dialkylimidazolium or the Fixanol;
B) by silicon ester, the sol-gel process of titanic acid ester is realized the loading or the bonding of Ti-Si composite oxide and catalytic active component.
Preparation of catalysts method of the present invention is characterized in that used silicon ester comprises (RO)
4Si, Cl (CH
2)
nSi (OR)
3, CH
3Si (OR)
3, CH
3OSi (OR)
3, CH
3CH
2Si (OR)
3, CH
3CH
2OSi (OR)
3, wherein R is C
1To C
4Various alkyl, n=0-6.
Preparation of catalysts method of the present invention is characterized in that used titanic acid ester comprises tetrabutyl titanate, isopropyl titanate, tetraethyl titanate.
Preparation of catalysts method of the present invention is characterized in that used palladium complex comprises that the chlorination phenanthrene coughs up the phosphorus palladium, and tetrafluoride boron two phenanthrene are coughed up the phosphorus palladium, the inferior palladium acid of chlorine ammonia, the acid of chlorine palladium.
Application of Catalyst of the present invention, it is characterized in that this catalyzer is 80 ℃ to 200 ℃ of temperature, oxygen is 0: 1 to 1: 2 with the carbon monoxide pressure ratio, and total pressure is catalysis nitrogenous compound oxonation system carbamate and 2-substituted carbamide under 1.0MPa to 7.0MPa condition.
The present invention realizes by following measure:
The canonical process of preparation catalyzer is among the present invention: be heated to room temperature to 150 ℃ under a certain amount of silicon ester is stirred, an amount of palladium complex joins in the silicon ester after being dissolved in suitable ionic liquid.Add immediately after stirring with the concentrated hydrochloric acid (12mol/l) or the vitriol oil (18mol/l), various sour dissolved titanic acid ester such as concentrated nitric acid (16mol/l) and Glacial acetic acid, water, required methyl alcohol or ethanol.This system generation polymerization after about 10 to 50 minutes continues under this temperature and wore out 3 to 24 hours.Vacuum-drying in 200 ℃, continued to obtain in aging 1 to 5 hour the compound oxycompound supported ionic liquid of required titanium silicon-palladium complex catalyzer after 0.5 to 5 hour under room temperature to the 150 ℃ condition under the 5.0MPa condition of nitrogen gas.
This catalyzer can be 80 ℃ to 200 ℃ of temperature, and oxygen is 0: 1 to 1: 2 with the carbon monoxide pressure ratio, and total pressure is efficient catalytic nitrogenous compound carbonylation system carbamate and 2-substituted carbamide reaction under 1.0MPa to 7.0MPa condition.
Compare with existing metal complex carbonylation catalyst, the substantive distinguishing features that the present invention has is:
1. this catalyzer is with ionic liquid, and metallo-organic complex and poromerics combine, and a kind of new way of homogeneous catalyst heterogenize is provided;
2. the content of palladium complex is relatively low in this catalyzer, has reduced the cost of catalyzer;
3. the ionic liquid consumption is lower and combine or be loaded into carrier among the hole of carrier with the form of chemical bond, palladium complex then by immobilized among ionic liquid, active ingredient is difficult for running off, and can reuse;
4. this catalyst system is active high, and its corresponding transformation frequency can reach more than the 10000mol/mol/h;
5. this catalyzer is solid granular, easy to usely separates with product;
6. this catalyzer can be realized the catalyzed oxidation oxonation of nitrogenous compound under lower temperature and pressure, has reduced energy consumption and to the requirement of reaction unit.
Embodiment
Embodiment 1:
Get the positive tetraethyl orthosilicate of 20ml, be heated to 60 ℃ in the 100ml Erlenmeyer flask.Take by weighing 60mg chlorination phenanthrene and cough up the phosphorus palladium, and transfer to rapidly in the positive tetraethyl orthosilicate in the 1ml chloridization 1-methyl-3-butyl imidazole.In this system, add the 4ml tetrabutyl titanate that is dissolved in the 4ml concentrated hydrochloric acid (12mol/l), 7ml distilled water, 15ml dehydrated alcohol, this system generation collosol and gel phenomenon after about 30 minutes then.Continue under this temperature and wore out 12 hours, water circulating pump vacuum-drying 3 hours, then at 200 ℃, the 5.0MPa nitrogen atmosphere was handled 3 hours down, got Ti-Si composite oxide supported ionic liquid-chlorination phenanthrene and coughed up phosphorus palladium catalyst 0.10%Pd-9.3%BMImCl/TiO
ySiO
x(a), titanium wherein, the mol ratio of silicon is 1: 7.6, ion liquid weight loading is 9.3%, shows that by Atomic Emission Spectral Analysis wherein the weight loading of palladium is 0.10%.
Embodiment 2:
Get the positive quanmethyl silicate of 20ml, in the 100ml Erlenmeyer flask, be stirred and heated to 100 ℃.Take by weighing 60mg chlorination phenanthrene and cough up the phosphorus palladium and be dissolved in 1ml chlorination 1-methyl-3-chlorobutyl imidazoles (CBMImCl), and transfer to rapidly in the positive quanmethyl silicate.In this system, add the 4ml tetrabutyl titanate that is dissolved in the 4ml concentrated hydrochloric acid (12mol/l), 7ml distilled water, 15ml anhydrous methanol, this system generation collosol and gel phenomenon after about 10 minutes then successively.Continue under this temperature and wore out 24 hours, water circulating pump vacuum-drying 3 hours, then at 200 ℃, the 5.0MPa nitrogen atmosphere was handled 3 hours down, obtained titanium silicon combined oxidation supported ionic liquid-Fei and coughed up phosphorus palladium catalyst 0.096%Pd-9.7%CBMImCl/TiO
y-SiO
x(b), titanium wherein, the mol ratio of silicon is 1: 7.6, and ion liquid weight loading is 9.7%, and Atomic Emission Spectral Analysis shows that wherein the weight loading of palladium is 0.096%.
Embodiment 3:
Step is with implementation example 2, but replaces the 4ml concentrated hydrochloric acid to be dissolved in the 4ml vitriol oil, catalyzer 0.089%Pd-9.3CBMImCl/TiO
y-SiO
x(c).Titanium wherein, silicon mol ratio is 1: 7.6, and ion liquid weight loading is 9.3%, and Atomic Emission Spectral Analysis shows that wherein the weight loading of palladium is 0.089%.
Embodiment 4:
Step is with implementation example 2, but to be dissolved in 1ml trifluoromethanesulfonic acid 1-methyl-3-butyl imidazole (BMImCF
3SO
3) 60mg chlorination phenanthrene cough up the 60mg chlorination phenanthrene that the phosphorus palladium replaces being dissolved in 1ml chlorination 1-methyl-3-chlorobutyl imidazoles (CBMImCl) and cough up the phosphorus palladium, catalyzer 0.092%Pd-9.1BMImCF
3SO
3/ TiO
y-SiO
x(d).Titanium wherein, silicon mol ratio is 1: 7.6, and ion liquid weight loading is 9.1%, and Atomic Emission Spectral Analysis shows that wherein the weight loading of palladium is 0.092%.
Embodiment 5:
Step is with implementation example 2, but replaces 60mg chlorination phenanthrene to cough up the phosphorus palladium with the inferior palladium acid of 30mg chlorine ammonia, catalyzer 0.093%Pd-9.9%CBMImCl/TiO
y-SiO
x(e).Titanium wherein, silicon mol ratio is 1: 7.6, and ion liquid weight loading is 9.9%, and Atomic Emission Spectral Analysis shows that wherein the weight loading of palladium is 0.093%.
Embodiment 6-10:
Be to add catalyzer a 0.5g in the reaction under high pressure axe of 500ml at volume successively, aniline 2.5ml charges into carbon monoxide 4.0MPa then, oxygen 1.0MPa.Airtight back was heated to 150 ℃ with 30 minutes continues to keep reaction 60 minutes, is cooled to that use HP6890/5973 gas chromatograph-mass spectrometer and 1790 gas chromatographs carry out qualitative and quantitative analysis (example 6) after the room temperature.
Replace catalyzer a with catalyzer b, c, d respectively, all the other are with example 6 (routine 7-9).
Replace 2.5ml aniline with the 2.5ml hexahydroaniline, replace catalyzer a with catalyzer e, all the other are with example 6 (example 10).
Table one aniline and hexahydroaniline oxidative carbonylation result
| Project | Reactant | Catalyzer | Transformation efficiency (%) | Selectivity (%) | Product |
| Embodiment 6 | Aniline | a | 96 | 96 | The anilino methyl-formiate |
| Embodiment 7 | Aniline | b | 91 | 89 | The anilino methyl-formiate |
| Embodiment 8 | Aniline | c | 83 | 93 | The anilino methyl-formiate |
| Embodiment 9 | Aniline | d | 87 | 91 | The anilino methyl-formiate |
| Embodiment 10 | Hexahydroaniline | e | 91 | 91 | Dicyclohexylurea (DCU) |
Claims (7)
1. microporous material carried metal organic complex-ionic-liquid catalyst, it is characterized in that metallo-organic complex and ionic liquid are by in the hole that is loaded into poromerics of high dispersive, form a kind of microcosmic homogeneous phase, macroscopical heterogenetic catalyst system, wherein used poromerics is a Ti-Si composite oxide, used metallo-organic complex is a palladium complex, used ionic liquid is 1,3-dialkylimidazolium or Fixanol; The loading of palladium is 0.04% to 3% of a titanium-silicon composite oxide carrier weight, and ion liquid loading is 1% to 15% of a vehicle weight, titanium in the Ti-Si composite oxide, and the mol ratio of silicon is for being 1: 50 to 1: 1.
2. as catalyzer as described in claims 1, it is characterized in that 1, the substituted alkyl chain length of 3-dialkylimidazolium or Fixanol is C
1To C
8Alkyl chain, the anionicsite of salt is a fluorine, chlorine, bromine, iodine, fluoroboric acid root, hexafluorophosphoric acid root, sulfate radical, nitrate radical, trifluoracetic acid root, trifluoromethanesulfonic acid root.
3. as Preparation of catalysts method as described in claims 1, it is characterized in that this method may further comprise the steps:
A) palladium complex dissolves or is complexed to 1, in 3-dialkylimidazolium or the Fixanol;
B) by silicon ester, the sol-gel process of titanic acid ester is realized the loading or the bonding of Ti-Si composite oxide and catalytic active component.
4. as claims 3 described methods, it is characterized in that used silicon ester comprises (RO)
4Si, Cl (CH
2)
nSi (OR)
3, CH
3Si (OR)
3, CH
3OSi (OR)
3, CH
3CH
2Si (OR)
3, CH
3CH
2OSi (OR)
3, wherein R is C
1To C
4Various alkyl, n=0-6.
5. as claims 3 described methods, it is characterized in that used titanic acid ester comprises tetrabutyl titanate, isopropyl titanate, tetraethyl titanate.
6. as claims 1 described method, it is characterized in that used palladium complex comprises that the chlorination phenanthrene coughs up the phosphorus palladium, tetrafluoride boron two phenanthrene are coughed up the phosphorus palladium, the inferior palladium acid of chlorine ammonia, the acid of chlorine palladium.
7. as Application of Catalyst as described in claims 1, it is characterized in that this catalyzer is 80 ℃ to 200 ℃ of temperature, oxygen is 0: 1 to 1: 2 with the carbon monoxide pressure ratio, and total pressure is catalysis nitrogenous compound oxonation system carbamate and 2-substituted carbamide under 1.0MPa to 7.0MPa condition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021195684A CN1150995C (en) | 2002-05-25 | 2002-05-25 | Microporous material carried metal complex-ionic liquid catalyst |
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|---|---|---|---|
| CNB021195684A CN1150995C (en) | 2002-05-25 | 2002-05-25 | Microporous material carried metal complex-ionic liquid catalyst |
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| CN1150995C true CN1150995C (en) | 2004-05-26 |
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| CN102343278A (en) * | 2011-07-20 | 2012-02-08 | 北京工业大学 | Method for preparing heterogeneous catalyst used for epoxy cyclohexane and application thereof |
| CN105642343B (en) * | 2014-11-10 | 2018-09-04 | 中国石油天然气股份有限公司 | A kind of load silicon type ionic-liquid catalyst |
| CN107226911A (en) * | 2017-07-31 | 2017-10-03 | 王琪宇 | A kind of preparation method for producing fabric softener polyether modified silicon oil |
| CN110506739A (en) * | 2019-09-16 | 2019-11-29 | 中国科学院海洋研究所 | A kind of double-bang firecracker of complex compound mixing package should discharge sterilization material and preparation method thereof |
| EP4029603A4 (en) * | 2019-11-12 | 2024-01-03 | Wanhua Chemical Group Co Ltd | Catalytic oxidation catalyst, preparation method therefor, and method for deep treatment of organic matters in mdi saline |
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