CN1446632A - Preparation of organic/inorganic nano media pores hybridization catalyst utilized for synthesizing methyl carbonate as well as its application - Google Patents
Preparation of organic/inorganic nano media pores hybridization catalyst utilized for synthesizing methyl carbonate as well as its application Download PDFInfo
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Abstract
A nano-class organic/inorganic mesoporous hybridizing catalyst for preparing dimethyl carbonate by liquid-phase oxidization and carbonylation of methanol contains copper halides and the carrier which is a nano-class organic/inorganic mesoporous hybridizing material with specially treated surface for effectively dispersing the copper halides on it. The said dimethyl carbonate is prepared from methanol, catalyst, CO and O2 through reaction at 110-140 deg.C and 2.0-5.0 MPa. Its advantages are high selectivity, activity and stability, low corrosion and cyclic use of catalyst.
Description
Technical field
The invention belongs to the preparation and the using method of the hybrid mesoporous composite catalyst of organic/inorganic nano that is used for the synthetic dimethyl carbonate of methanol solution phase oxidation carbonylation.
Background technology
As a kind of novel organic worker raw material with high added value, synthetic and the application study of dimethyl carbonate (DMC) cause people's extensive concern in recent years.Dimethyl carbonate is described as " green " chemical products and chemical synthesis " new matrix ", because of it has high activity, can replace severe toxicity and carcinogenic phosgene, dimethyl suflfate to make many valuable chemical products, be widely used in the synthetic of high performance resin, medicine, pesticide intermediate as carbonylation agent, methylating reagent etc.; Alternative various toxic solvent is as the solvent of coating, paint; Because of having high oxygen content, replacing methyl tertiary butyl ether(MTBE) (MTBE) to do aspect the gasoline additive very wide prospect is arranged also.The traditional industry of dimethyl carbonate is produced and is adopted the phosgenation technology path because the phosgene severe toxicity, etching apparatus, and product quality is relatively poor, in a short time will be fully by with methyl alcohol, CO and O
2Methanol oxidation carbonyl process (comprising liquid phase method and vapor phase method) institute replacement fully for raw material.Oxidative carbonylation of methanol method is a kind of new technology route of synthetic DMC, tool advantage on Technological Economy, advantage such as this technology is compared with traditional phosgenation, has raw material to be easy to get, and technology is simple, and three-waste free pollution and production cost are low, quality is good.Italy Eni Chem company is catalyst with the stannous chloride, takes the lead in the technology of synthesizing methyl carbonate by methanol liquid phase oxidation oxonation has been realized industrialization (Ind.Chim.21 (1), 1985) mid-term in the eighties.But stannous chloride (CuCl) has severe corrosive to reaction unit, must add anti-corrosion materials such as upper glass or enamel lining at reactor wall, makes that device is difficult to realize maximizing.In addition, because the dissolubility extreme difference of CuCl in reaction system must use the CuCl of high concentration to obtain enough reaction speeds in the Eni Chem technology.Chinese patent CN1197792A (1998) is major catalyst with CuCl, magnesium chloride, calcium chloride etc. are auxiliary agent, prepare the composite catalyst of alkaline-earth metal salt decorative, improved the dissolubility of stannous chloride in reactant liquor to a certain extent, improved catalyst activity, but do not had to solve etching problem equipment.Chinese patent CN1333086A (2002) has announced with CuCl to be major catalyst, with the nitrogenous heterocyclic compound or the composite catalyst of high-molecular complex formation, further improved the dissolubility of stannous chloride in reactant liquor, catalyst activity and selectivity have been improved, and reaction system is decreased to the corrosivity of equipment, still have to be solved but the use amount of catalyst reaches technical problems such as stability greatly.
Meanwhile, have more the industrialization meaning, the immobilized interest that in recent years causes people very big of catalyst on inorganic oxide carrier for making catalyst.U.S. Pat 5093513 (1992) has been announced with CuCl
2Be major catalyst, through (EtO)
3Si (CH
2)
3NH
2Or (EtO)
3Si (CH
2)
3NHCH
2CH
2NH
2The carrier loaded composite hybridization catalyst of the common amorphous silicon oxide of finishing is used for liquid phase methanol oxidation carbonylation Synthesis of dimethyl carbonate, make catalyst have the advantage of homogeneous phase and heterogeneous catalyst in actual use simultaneously concurrently, but it is to be noted that above-mentioned catalyst system and catalyzing also exists reaction efficiency lower and problem such as be difficult to be repeatedly used.
Summary of the invention
The objective of the invention is to propose that a kind of reaction efficiency is higher, catalytic performance is stable, preparation technology is simple, can be repeatedly used, and selectively is used for the hybrid mesoporous composite catalyst of novel organic/inorganic nano of methanol oxidation carbonylation preparing dimethyl carbonate.
The hybrid mesoporous composite catalyst of organic/inorganic nano that is used for the synthetic dimethyl carbonate of methanol oxidation carbonylation that the present invention proposes, the nanometer mesoporous silicon oxide material that employing has series such as MCM, the HMS of one dimension or the regular pore passage structure of bidimensional nanometer or SBA is a novel carriers, utilizes bonding action with a large amount of functionalized organosilan molecules (EtO)
3Si (CH
2)
3NHCHO or (EtO)
3Si (CH
2)
3NCHOCH
2CH
2The direct grafting of NHCHO is to the mesoporous nano carrier surface, the functionalized hybrid mesoporous carriers of organic/inorganic nano such as (NHCHO) that obtains having amide group.On this basis further with copper chloride (CuCl
2) or stannous chloride copper ion halide such as (CuCl) carry out compoundly, finally obtain can be used for the hybrid mesoporous catalyst of efficient nano of the synthetic dimethyl carbonate of methanol oxidation carbonylation.As everyone knows, copper chloride (CuCl in Eni Chem technology
2) or chlorination press copper (CuCl) activity lower, therefore need in actual use to remedy this deficiency by increasing the catalyst use amount greatly, also brought problems such as heavy corrosion simultaneously to consersion unit.On the functionalized mesoporous nano carrier of the employing amide group that the present invention proposes distinctive organic ligands such as nitrogenous, the oxygen of immobilized amide group with strong electron donation, can significantly improve the catalytic efficiency of copper catalyst by the novel hybrid catalyst that complexing forms with copper ion halide such as copper chloride or stannous chlorides.In addition and since the mesoporous nano carrier surface immobilized amino and amide group have stronger alkalescence, make the acidity of composite catalyst also greatly reduce.Therefore, the hybrid mesoporous composite catalyst of this organic/inorganic nano can significantly improve the selectivity of conversion of methanol and dimethyl carbonate, and the corrosivity to reactor is very low simultaneously, can be without corrosion-proof lining.
Catalyst characteristics of the present invention is that the hybridization mesoporous material that a kind of organic alcoxyl silane that contains organo-functional group and nanometer mesoporous silicon oxide form is a carrier, the immobilized copper ion of this carrier, the organo-functional group that wherein organic alcoxyl silane contains is heteroatomic active organic groups such as nitrogenous and oxygen such as acid amides or pyridine, and its content in carrier is 5～10wt%; Nanometer mesoporous silicon oxide is the MCM series mesoporous material with regular one dimension or bidimensional nano pore, and as MCM-41, MCM-48, HMS and SBA series material are as SBA-15, SBA-12 etc.; Copper halide such as CuCl, CuCl
2, CuI, CuBr
2, CuBr etc., the content of copper ion in carrier is 3～10wt% scope.The average duct of catalyst of the present invention is 2～30 nanometers.
Preparation of catalysts method of the present invention is: will contain organic alcoxyl silane of organic functional group and be dispersed in the solvent stirring and refluxing 10～12 hours through the nanometer mesoporous silicon oxides of 200 ℃ of pre-dehydrations, and obtain the mesoporous material of hydridization; With the mesoporous material of above-mentioned hydridization and copper halide stirring and refluxing 5～10 hours in alcoholic solution, vacuum drying gets final product.Solvent can get final product by the solubilizing reaction thing during above-mentioned hydridization, as toluene, dimethylbenzene etc., with copper halide stirring and refluxing in alcoholic solution can be methyl alcohol, ethanol equal solvent.The molar concentration ratio of each reactant is in the above-mentioned preparation process: the organic alcoxyl silane that contains organic functional group: nanometer mesoporous silicon oxide=1: 4～20; Hybridization mesoporous material: copper halide=1: 6～30.
Above-mentioned reactant contains organic alcoxyl silane of organic functional group and can directly buy, also can get by amidatioon of organic alcoxyl silane or pyridine reaction, as take by weighing a certain amount of mesopore silicon oxide samples (MCM-41, HMS or SBA-15 etc.) through 200 ℃ of pre-dehydrations and add and be dissolved with in the toluene solution of a certain amount of aminopropyl triethoxysilane and Ethyl formate, then above-mentioned mixed liquor stirring and refluxing is obtained the supported hybridization mesoporous material of amide group.With the supported hybridization mesoporous material of above-mentioned amide group and copper chloride or stannous chloride stirring and refluxing in ethanolic solution, obtain the hybrid mesoporous composite catalyst of organic/inorganic nano again through vacuum drying.
Among the present invention copper halide get anion be Cl, Br or I ion all can, as CuCl
2, CuBr, CuI etc.With the mesoporous material SBA-15 is example, can obtain the hybrid mesoporous composite catalyst of organic/inorganic nano of about 2～30 nanometers in aperture by above-mentioned preparation method.What accompanying drawing 1 provided is the stereoscan photograph of SBA-15 carrier material, and this material presents more regular fascicular texture on macro-scale, and this material becomes less granular texture (Fig. 2) behind the amide group surface graft.Fig. 3 is the transmission electron microscope photo of the SBA-15 hybrid mesoporous composite catalyst of immobilized stannous chloride organic/inorganic nano on different high preferred orientations with Fig. 4 demonstration, can be clear that this mesoporous nano hybrid catalyst is still keeping the regular bidimensional hexagonal hole road structure of about 7 nanometers of channel diameter.Fig. 5 has provided the transmitted infrared light spectrum of the hybrid mesoporous composite catalyst of the immobilized stannous chloride organic/inorganic nano of SBA-15 in its preparation different phase.Infrared data shows that mesoporous nano catalyst surface bonding has a large amount of amide groups organic groups, and copper ion makes the remarkable red shift of ultra-red vibration frequency of this group, illustrates that copper ion and amide group exist stronger coordination to interact.
The concrete implementing procedure that the hybrid mesoporous composite catalyst of organic/inorganic nano proposed by the invention is used for the synthetic dimethyl carbonate of methanol solution phase oxidation carbonylation is: at first a certain amount of methyl alcohol and mesoporous nano hydridization composite catalyst are added reactor, stirring fully mixes it, adopt gas once to add then or add modes such as reactor continuously, with the CO/O of certain oxygen content
2Gaseous mixture feeds reactor, utilizes gas to keep reaction pressure, with the heating of heating jacket electric furnace, when the still temperature is 100～160 ℃, is constantly reacting under the condition of stirring.Stop ventilation after reaction finishes, reactant liquor is shifted out, adopt simple distillation to get CH
3The OH-DMC azeotropic mixture carries out special distillation (extractive distillation, azeotropic distillation, distillation under pressure) to this azeotropic mixture, obtains the DMC product and reclaims CH
3OH.
The present invention implements the reaction of the synthetic dimethyl carbonate of methanol solution phase oxidation carbonylation in the 500ml batch autoclave, suitable reaction process condition is: 90～140 ℃ of temperature, pressure 1.0～5.0MPa, methanol usage 50～200ml, catalyst amount 1～10 gram, reaction time 30～300min, unstripped gas (CO+O
2) in oxygen content be 5～20%.The product gas chromatographic analysis.Catalyst productivity is 1.0～4gDMC/gcath, dimethyl carbonate selectivity 〉=99.5%.
Characteristics of the present invention are catalyst activity and selectivity height, performance and Stability Analysis of Structures, and can be repeatedly used.
Description of drawings Fig. 1 is ESEM (SEM) figure of SBA-15 carrier material.Fig. 2 is ESEM (SEM) figure of above-mentioned hybrid material behind the amide group surface graft.Fig. 3 is transmission electron microscope (TEM) figure behind the immobilized cuprous chloride catalyst of SBA-15.Fig. 4 is transmission electron microscope (TEM) figure behind the immobilized cuprous chloride catalyst of SBA-15.Fig. 5 be the immobilized cuprous chloride catalyst of SBA-15 different preparatory phases transmission infrared (IR) spectrogram.
The specific embodiment
Embodiment one
To in the toluene that the adding of the 10g MCM-41 sample behind 200 ℃ of preliminary treatment 10h 100mL newly steamed, after stirring, add 40mL (EtO)
3Si (CH
2)
3NH
2With the mixture of 50mL anhydrous formic acid ethyl ester, be heated to 120 ℃, continue stirring and refluxing 12h, with absolute ethyl alcohol repeatedly wash, suction filtration is placed on vacuumizing and drying in the vacuum drying chamber; Above-mentioned product is added in the 100mL ethanol, add 3g CuCl again
2, stirring and refluxing 10h with absolute ethyl alcohol washing reaction product repeatedly, promptly gets 12g CuCl after the vacuum drying
2-amide-MCM-41 mesoporous nano hybrid catalyst (Cu content: 3wt%).
In the 500ml autoclave, add 100ml methyl alcohol, 8g CuCl
2-amide-MCM-41 mesoporous nano hybrid catalyst is with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 3 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 99.7%, catalyst productivity 1.0gDMC/gcath.
Embodiment two
To in the toluene that the adding of the 4g MCM-41 sample behind 200 ℃ of preliminary treatment 10h 100mL newly steamed, after stirring, add 40mL (EtO)
3Si (CH
2)
3NHCH
2CH
2NH
2With the mixture of 50mL anhydrous formic acid ethyl ester, be heated to 120 ℃, continue stirring and refluxing 12h, with absolute ethyl alcohol repeatedly wash, suction filtration is placed on vacuumizing and drying in the vacuum drying chamber; Above-mentioned product is added in the 100mL ethanol, add 3g CuCl again
2, stirring and refluxing 10h with absolute ethyl alcohol washing reaction product repeatedly, promptly gets 12gCuCl after the vacuum drying
2-diamide-MCM-41 mesoporous nano hybrid catalyst (Cu content: 10wt%).
In the 500ml autoclave, add 100ml methyl alcohol, 8g CuCl
2-diamide-MCM-41 mesoporous nano hybrid catalyst is with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 3 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 99.7%, catalyst productivity 1.2gDMC/gcath.
The comparative example one
In the 500ml autoclave, add 100ml methyl alcohol, 8g CuCl
2, with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 2 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 94.7%, catalyst productivity 0.5gDMC/gcath.
Embodiment three
To in the toluene that the adding of the 10g HMS sample behind 200 ℃ of preliminary treatment 10h 100mL newly steamed, after stirring, add 40mL (EtO)
3Si (CH
2)
3NHCH
2CH
2NH
2With the mixture of 50mL anhydrous formic acid ethyl ester, be heated to 120 ℃, continue stirring and refluxing 12h, with absolute ethyl alcohol repeatedly wash, suction filtration is placed on vacuumizing and drying in the vacuum drying chamber; Above-mentioned product is added in the 100mL ethanol, add 5g CuCl again, stirring and refluxing 10h with absolute ethyl alcohol washing reaction product repeatedly, promptly gets 12g CuCl-diamide-HMS mesoporous nano hybrid catalyst (Cu content: 4wt%) after the vacuum drying.
Add 100ml methyl alcohol in the 500ml autoclave, 8g CuCl-diamide-HMS mesoporous nano hybrid catalyst is with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 4 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 99.7%, catalyst productivity 2.5gDMC/gcath.
Embodiment four
To in the toluene that the adding of the 10g SBA-15 sample behind 200 ℃ of preliminary treatment 10h 100mL newly steamed, after stirring, add 40mL (EtO)
3Si (CH
2)
3NCHOCH
2CH
2NHCHO is heated to 120 ℃, continues stirring and refluxing 12h, with absolute ethyl alcohol repeatedly wash, suction filtration is placed on vacuumizing and drying in the vacuum drying chamber; Above-mentioned product is added in the 100mL ethanol, add 3g CuCl again
2, stirring and refluxing 10h with absolute ethyl alcohol washing reaction product repeatedly, promptly gets 12g CuCl after the vacuum drying
2-diamide-SBA-15 mesoporous nano hybrid catalyst (Cu content: 5wt%).
In the 500ml autoclave, add 100ml methyl alcohol, 8g CuC1
2-diamide-SBA-15 mesoporous nano hybrid catalyst is with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 4 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 99.7%, catalyst productivity 2.0gDMC/gcath.
Embodiment five
To in the toluene that the adding of the 10g SBA-15 sample behind 200 ℃ of preliminary treatment 10h 100mL newly steamed, after stirring, add 40mL pyridine organosilan (EtO)
3Si (CH
2)
3(C
5H
4N), be heated to 120 ℃, continue stirring and refluxing 12h, with absolute ethyl alcohol repeatedly wash, suction filtration is placed on vacuumizing and drying in the vacuum drying chamber; Above-mentioned product is added in the 100mL ethanol, add 5g CuCl again, stirring and refluxing 10h with absolute ethyl alcohol washing reaction product repeatedly, promptly gets 12g CuCl-Py-SBA-15 mesoporous nano hybrid catalyst (Cu content: 3wt%) after the vacuum drying.
Add 100ml methyl alcohol in the 500ml autoclave, 8g CuCl-amide-SBA-15 mesoporous nano hybrid catalyst is with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 4 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 99.7%, catalyst productivity 2.5gDMC/gcath.
Embodiment six
To in the toluene that the adding of the 10g SBA-15 sample behind 200 ℃ of preliminary treatment 10h 100mL newly steamed, after stirring, add 40mL (EtO)
3Si (CH
2)
3NHCH
2CH
2NH
2With the mixture of 50mL anhydrous formic acid ethyl ester, be heated to 120 ℃, continue stirring and refluxing 12h, with absolute ethyl alcohol repeatedly wash, suction filtration is placed on vacuumizing and drying in the vacuum drying chamber; Above-mentioned product is added in the 100mL ethanol, add 5g CuCl again, stirring and refluxing 10h with absolute ethyl alcohol washing reaction product repeatedly, promptly gets 12gCuCl-diamide-SBA-15 mesoporous nano hybrid catalyst (Cu content: 5wt%) after the vacuum drying.
Add 100ml methyl alcohol in the 500ml autoclave, 8g CuCl-diamide-SBA-15 mesoporous nano hybrid catalyst is with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 4 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 99.7%, catalyst productivity 3.5gDMC/gcath.
Embodiment seven
Add 100ml methyl alcohol in the 500ml autoclave, used CuCl-diamide-SBA-15 mesoporous nano hybrid catalyst among the 8g embodiment six is with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.140 ℃ of reactions 4 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 99.7%, catalyst productivity 4.3gDMC/gcath.
Embodiment eight
Add 100ml methyl alcohol in the 500ml autoclave, used CuCl-diamide-SBA-15 mesoporous nano hybrid catalyst among the 8g embodiment six is with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.90 ℃ of reactions 4 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 99.7%, catalyst productivity 2.1gDMC/gcath.
Claims (4)
1. the hybrid mesoporous catalyst of the organic/inorganic nano of a Synthesis of dimethyl carbonate contains organic alcoxyl silane of organic functional group and hybrid material that nanometer mesoporous silicon oxide forms is a carrier with a kind of, and the immobilized copper ion of this carrier is characterized in that:
(1) organo-functional group that contains of organic alcoxyl silane is acid amides or pyridine group, and its content in carrier is 5～20wt%;
(2) nanometer mesoporous silicon oxide is MCM, HMS or the SBA series mesoporous material with regular one dimension or bidimensional nano pore;
(3) content of copper ion in carrier is 3～10wt%;
(4) the average channel diameter of this catalyst is 2～30 nanometers.
2. the hybrid mesoporous catalyst of the organic/inorganic nano of Synthesis of dimethyl carbonate according to claim 1 is characterized in that this Preparation of catalysts method is:
(1) a certain proportion of organic alcoxyl silane and nanometer mesoporous silicon oxide that contains organic functional group is dispersed in the toluene equal solvent;
(2) above-mentioned mixed system stirring and refluxing is 10～12 hours, gets hybridization mesoporous material;
(3), wash repeatedly through methyl alcohol that final vacuum is dry to get final product with above-mentioned hybridization mesoporous material and copper halide stirring and refluxing 5～10 hours in alcoholic solution;
(4) reactant molar concentration ratio is in the above steps:
The organic alcoxyl silane that contains organic functional group: nanometer mesoporous silicon oxide=1: 4～20;
Hybridization mesoporous material: copper halide=1: 6～30.
3. the hybrid mesoporous catalyst of the organic/inorganic nano of Synthesis of dimethyl carbonate as claimed in claim 2, it is characterized in that containing organic functional group, to get organic alcoxyl silane be to make by amidatioon of organic alcoxyl silane and pyridine reaction.
4. the hybrid mesoporous catalyst of the organic/inorganic nano of Synthesis of dimethyl carbonate according to claim 2, the cation that it is characterized in that copper halide is Cu (II) or Cu (I) ion, anion is Cl, Br or I ion.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229534A (en) * | 2011-05-11 | 2011-11-02 | 武汉工程大学 | Method for synthesizing alkyl carbonic ester |
| CN107199051A (en) * | 2017-05-10 | 2017-09-26 | 中国科学院福建物质结构研究所 | A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof |
-
2003
- 2003-02-07 CN CNB031153291A patent/CN1168537C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229534A (en) * | 2011-05-11 | 2011-11-02 | 武汉工程大学 | Method for synthesizing alkyl carbonic ester |
| CN102229534B (en) * | 2011-05-11 | 2013-10-30 | 武汉工程大学 | Method for synthesizing alkyl carbonic ester |
| CN107199051A (en) * | 2017-05-10 | 2017-09-26 | 中国科学院福建物质结构研究所 | A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof |
| CN107199051B (en) * | 2017-05-10 | 2019-11-26 | 中国科学院福建物质结构研究所 | A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof |
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