CN1376665A - High-molecular complex as catalyst for synthesizing dimethyl carbonate and its preparing process and application - Google Patents
High-molecular complex as catalyst for synthesizing dimethyl carbonate and its preparing process and application Download PDFInfo
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- CN1376665A CN1376665A CN 02111269 CN02111269A CN1376665A CN 1376665 A CN1376665 A CN 1376665A CN 02111269 CN02111269 CN 02111269 CN 02111269 A CN02111269 A CN 02111269A CN 1376665 A CN1376665 A CN 1376665A
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Abstract
A catalyst for synthesizing dimethyl carbonate is a complex prepared from copper halide and the high-molecular compound containing one or more heteroatoms (N, O, S, etc). Said dimethyl carbonate is synthesized through adding methanol, catalyst, CO and O2 to high-pressure reactor, and reacting at 90-160 deg.C and 1-5 MPa. The conversion rate of methanol is higher than 35%. The selectivity of target product is higher than 99.5%. Said catalyst features high activity, selectivity and stability, and low corrosion.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of high-molecular complex as catalyst and preparation and using method that is used for the synthetic methylcarbonate of methanol solution phase oxidation carbonylation.
Background technology
Methylcarbonate (DMC) is a kind of novel organic worker raw material with high added value, is described as " the new matrix " of " green " Chemicals and chemosynthesis.Because of it has high reactivity, can replace severe toxicity and carcinogenic phosgene, methyl-sulfate to make many valuable chemical products as carbonylation agent, methylating reagent etc., be widely used in the synthetic of performance resins, medicine, pesticide intermediate; Alternative various noxious solvent is as the solvent of coating, paint; Because of having high oxygen level, replacing methyl tertiary butyl ether (MTBE) to do aspect the gasoline dope very wide prospect is arranged also.The preparation method of methylcarbonate has phosgenation, ester-interchange method and methanol oxidation carbonyl process (comprising liquid phase method and vapor phase process).In industrialized production technology, phosgenation is because the phosgene severe toxicity, etching apparatus, and quality product is relatively poor, and in a short time will the replacement fully of complete oxidized carbonyl compound established law institute.With methyl alcohol, CO and O
2For the oxidative carbonylation of methanol method of raw material 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 catalyzer with the cuprous 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 cuprous chloride (CuCl) has severe corrosive to reaction unit, must add impregnating material such as upper glass or enamel lining at reactor wall, makes that device is difficult to realize maximizing.In addition, because the solvability extreme difference of CuCl in reaction system must use the CuCl of high density to obtain enough speed of response in the Eni chem technology.Chinese patent CN1197792A (1998) is Primary Catalysts with CuCl, magnesium chloride, calcium chloride etc. are auxiliary agent, prepare the composite catalyst of alkaline-earth metal salt decorative, improved the solvability of cuprous chloride in reaction solution 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 Primary Catalysts, with the nitrogenous heterogeneous ring compound or the composite catalyst of high-molecular complex formation, further improved the solvability of cuprous chloride in reaction solution, catalyst activity and selectivity have been improved, and reaction system is decreased to the corrodibility of equipment, still have to be solved but the usage quantity of catalyzer reaches technical problems such as stability greatly.
Summary of the invention
The objective of the invention is to propose a kind of raw material more be simple and easy to, simple, the long service life of preparation technology, and high reactivity is arranged and optionally is used for novel high polymer complex compound catalyst and the preparation and the using method of methanol oxidation carbonylation preparing dimethyl carbonate.
The high-molecular complex as catalyst that is used for the synthetic methylcarbonate of methanol oxidation carbonylation that the present invention proposes adopts divalence Cu (II) system that has good stability to replace monovalence Cu (I), and with the lower Br of corrodibility
-Replaced C l
-But well-known, cupric catalyst system such as cupric chloride (CuCl
2) its activity is inferior to monovalence CuCl system with selectivity in the synthetic dimethyl carbonate of liquid phase methanol oxidation carbonylation, so one or more heteroatomic high molecular polymers with strong electron donation such as that the present invention proposes to adopt is nitrogenous, oxygen and sulphur are part, make catalyzer with the high-molecular complex that the divalence copper halide forms, implement the reaction of the synthetic methylcarbonate of methanol solution phase oxidation carbonylation, can avoid aforementioned deficiency.Copper in the catalyzer/heteroatoms mol ratio can be 1: 0.2～l: l0.
Among the present invention, copper halide adopts one or both combination of cupric chloride or cupric bromide, will stablize and easy to use more than cuprous chloride (CuCl).Used contain one or more the combination that heteroatomic high molecular polymer can be water-soluble or half water soluble polymer such as polyoxyethylene glycol, polyvinyl pyridine, polyacrylamide, polyaniline, Polythiophene and polythiourea.
The invention allows for the preparation method of above-mentioned complex compound catalyst, concrete steps are: take by weighing a certain amount of heteroatomic high molecular polymer and the second order copper halide of containing, be dissolved in jointly in methyl alcohol or the tetrahydrofuran (THF) equal solvent, wherein copper and heteroatomic mol ratio are l: 0.2-l: 10, and the concentration of solution is the 0.01-1.0 mol; In 70-90 ℃ of backflow 10-15 hour, slow evaporate to dryness under 40～80 ℃ of reduced pressure promptly got brown Powdered copper halide-high-molecular complex as catalyst then with above-mentioned mixed solution.Above-mentioned second order copper halide is the combination of a kind of of cupric chloride or cupric bromide or two kinds, contains the heteroatoms high molecular polymer and be one or more combination of water-soluble or half water soluble polymer such as polyoxyethylene glycol, polyvinyl pyridine, polyacrylamide, polyaniline, Polythiophene and polythiourea.
The invention allows for above-mentioned high-molecular complex as catalyst and be used for the method that methanol solution phase oxidation carbonylation synthesizes methylcarbonate, concrete steps are: at first a certain amount of methyl alcohol and high-molecular complex as catalyst are added in the reactor, stir, make its thorough mixing, feed CO+O then
2Mixed gas utilizes gas to keep reaction pressure, and heating when the still temperature is 90～160 ℃, is under agitation reacted.Stop ventilation after reaction finishes, reaction solution is shifted out, distillation gets CH
3The OH-DMC azeotrope carries out special distillation (for example extractive distillation, component distillation, pressure distillation etc.) to this azeotrope again, promptly obtains the DMC product, and reclaims CH
3OH.
In the above-mentioned using method, implement the reaction of the synthetic methylcarbonate of methanol solution phase oxidation carbonylation in the 500ml batch autoclave, suitable reaction process condition is: 90～160 ℃ of temperature, pressure 1.0～5.0MPa, methanol usage 50～200ml, catalyst levels 1～10 gram, unstripped gas CO+O
2Middle oxygen level is 5～20%, reaction times 30～300min.The reaction product gas chromatographic analysis.Catalyst productivity is 0.5～4gDMC/gcath, methylcarbonate selectivity 〉=99.5%.
The catalyst preparation process that the present invention proposes is simple, and active high, the selectivity stability is good, and catalyst structure is stable, and continuous operation is non-inactivation more than 1000 hours.This high-molecular complex as catalyst can improve the selectivity of conversion of methanol and methylcarbonate, and the corrodibility to reactor is very low simultaneously, can be without corrosion-proof lining.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1, take by weighing the 4.4g polyoxyethylene glycol (PEG, MW20000) and 17.0g CuCl
22H
2O is dissolved in respectively in the 50ml methyl alcohol, and is then that both are mixed and in 80 ℃ of backflow 12h, then at 60 ℃ of slow evaporates to dryness, promptly gets the brown Powdered CuCl of 21.0g
2-polyethyleneglycol catalyst.
Embodiment 2, in the 500ml autoclave, add 100ml methyl alcohol, 8g CuCl
2-polyethyleneglycol catalyst (Cu/O=1/2) is with mixed gas (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 120 minutes.The cooling back is with gas chromatographic analysis.Methylcarbonate selectivity 99.7%, catalyst productivity 1.0gDMC/gcath.
The comparative example 1, adds 100ml methyl alcohol, 8g CuCl in the 500ml autoclave
2, with mixed gas (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 120 minutes.The cooling back is with gas chromatographic analysis.Methylcarbonate selectivity 94.7%, catalyst productivity 0.5gDMC/gcath.
Embodiment 3, in the 500ml autoclave, add 100ml methyl alcohol, 8g CuCl
2-polyoxyethylene glycol complex compound catalyst (Cu/O=1/2) is with mixed gas (O
2: 16%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 120 minutes.The cooling back is with gas chromatographic analysis.Methylcarbonate selectivity 99.7%, catalyst productivity 2.0gDMC/gcath.
Embodiment 4, use 8g CuBr
2-polyvinyl pyridine complex compound (Cu/N=1/2) is made catalyzer, and all the other conditions are with embodiment 2, and the methylcarbonate selectivity is 99.4%, and catalyst productivity is 1.5gDMC/gcath.
Embodiment 5, use 8g CuCl
2-polyvinyl pyridine complex compound (Cu/N=1/2) is made catalyzer, and all the other conditions are with embodiment 3, and the methylcarbonate selectivity is 99.6%, and catalyst productivity is 3.0g DMC/gcath.
Embodiment 6, use 4g CuCl
2-polyvinyl pyridine complex compound (Cu/N=1/2) and 4g CuCl
2-polyoxyethylene glycol complex compound (Cu/O=1/2) is made catalyzer, and all the other conditions are with embodiment 2, and the methylcarbonate selectivity is 99.5%, and catalyst productivity is 2.0gDMC/gcath.
Embodiment 7, use 4g CuCl
2-polyvinyl pyridine complex compound (Cu/N=1/2) and 4g CuBr
2-polyoxyethylene glycol complex compound (Cu/O=1) is made catalyzer, and all the other conditions are with embodiment 3, and the methylcarbonate selectivity is 99.5%, and catalyst productivity is 3.5gDMC/gcath.
Claims (5)
1, a kind of high-molecular complex as catalyst that is used for the synthetic methylcarbonate of methanol solution phase oxidation carbonylation, it is characterized in that adopting one or more heteroatomic high molecular polymers with strong electron donation of nitrogenous, oxygen and sulphur is part, form by coordination with the second order copper halide, copper/heteroatomic mol ratio is 1: 0.2-1: 10.
2, high-molecular complex as catalyst according to claim 1 is characterized in that described second order copper halide is the combination of a kind of of cupric chloride, cupric bromide or two kinds.
3, high-molecular complex as catalyst according to claim 1 and 2 is characterized in that described heteroatoms high molecular polymer is polyoxyethylene glycol, polyvinyl pyridine, polyacrylamide, poly-methylamine, Polythiophene and polythiourea is water-soluble or one or more combination of half water soluble polymer.
4, a kind of preparation method of high-molecular complex as catalyst as claimed in claim 1, it is characterized in that concrete steps are: take by weighing a certain amount of heteroatoms high molecular polymer and second order copper halide of containing, be dissolved in jointly in methyl alcohol or the tetrahydrofuran solvent, with mixed solution in 70 ℃-90 ℃ backflow 10-15 hour, slow evaporate to dryness under 40-80 ℃ of reduced pressure promptly gets required catalyzer then.
5, a kind of using method of high-molecular complex as catalyst as claimed in claim 1 is characterized in that concrete steps are: at first methyl alcohol and catalyzer are added in the reactor, stir, make its thorough mixing; Feed CO+O then
2Mixed gas utilizes gas to keep reaction pressure, is heated to 90-160 ℃ of still temperature, under agitation reacts; Stop ventilation after reaction finishes, reaction solution is shifted out, distillation gets CH
3The OH-DMC azeotrope; Again azeotrope is carried out special distillation, promptly get the DMC product, and reclaim CH
3OH; Wherein, the consumption of methyl alcohol is 50-200ml, and catalyst levels is the 1-10 gram, CO+O
2Mixed gas in oxygen level be 5-20%, pressure is 1.0-5.OMpa, reaction times 30-300 minute.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB02111269XA CN1169624C (en) | 2002-04-04 | 2002-04-04 | High-molecular complex as catalyst for synthesizing dimethyl carbonate and its preparing process and application |
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| CNB02111269XA CN1169624C (en) | 2002-04-04 | 2002-04-04 | High-molecular complex as catalyst for synthesizing dimethyl carbonate and its preparing process and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388978C (en) * | 2005-12-26 | 2008-05-21 | 南京工业大学 | Complex catalyst for synthesizing carbonic ester by alcohol homogeneous oxidation carbonylation and preparation process and use method thereof |
| CN105080610A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院成都有机化学有限公司 | Process for preparing dimethyl carbonate catalyst by liquid-phase oxidation carbonylation of methanol |
| CN112236509A (en) * | 2018-06-12 | 2021-01-15 | 伊戈尔·斯坦提尼 | Multifunctional poly methylamine surfactant and preparation method thereof |
-
2002
- 2002-04-04 CN CNB02111269XA patent/CN1169624C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388978C (en) * | 2005-12-26 | 2008-05-21 | 南京工业大学 | Complex catalyst for synthesizing carbonic ester by alcohol homogeneous oxidation carbonylation and preparation process and use method thereof |
| CN105080610A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院成都有机化学有限公司 | Process for preparing dimethyl carbonate catalyst by liquid-phase oxidation carbonylation of methanol |
| CN112236509A (en) * | 2018-06-12 | 2021-01-15 | 伊戈尔·斯坦提尼 | Multifunctional poly methylamine surfactant and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1169624C (en) | 2004-10-06 |
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