CN102649757A - Method for producing dimethyl carbonate through CO coupling - Google Patents
Method for producing dimethyl carbonate through CO coupling Download PDFInfo
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- CN102649757A CN102649757A CN2011100465503A CN201110046550A CN102649757A CN 102649757 A CN102649757 A CN 102649757A CN 2011100465503 A CN2011100465503 A CN 2011100465503A CN 201110046550 A CN201110046550 A CN 201110046550A CN 102649757 A CN102649757 A CN 102649757A
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Abstract
The invention relates to a method for producing dimethyl carbonate through CO coupling, and mainly solves the technical problem of low selectivity of a target product existing in the prior art. The method comprises the following steps of: (a) feeding methyl nitrite-containing gas and a CO raw material into a first reaction region to contact with a palladium-containing catalyst I to produce a first stream of reaction effluent containing unreacted methyl nitrite, CO and product dimethyl carbonate; and (b) feeding the first stream of reaction effluent into a gas-liquid separator, feeding a liquid-phase product obtained by gas-liquid separation into a subsequent separation system to separate to obtain the dimethyl carbonate product, feeding a gas-phase mixture obtained by the gas-liquid separation into at least one second reaction region to contact with a palladium-containing catalyst II to produce a second stream of reaction effluent containing the dimethyl carbonate, wherein the molar ratio of the raw material CO to the methyl nitrite at the first reaction region is 0.5-3:1. According to the technical scheme, the problem is solved well; and the method can be used in industrial production for increasing the yield of the dimethyl carbonate.
Description
Technical field
The present invention relates to a kind of method of CO coupling production methylcarbonate, particularly about the method for CO and methyl nitrite coupling production methylcarbonate.
Background technology
Methylcarbonate abbreviation DMC is a kind of water white transparency during normal temperature, omit scent of, little sweet liquid, 4 ℃ of fusing points, 90.1 ℃ of boiling points, density 1.069g/cm
3, be insoluble in water, but can with nearly all immiscible organic solvents such as alcohol, ether, ketone.DMC toxicity is very low, is just classified as nontoxic product by Europe in 1992, be a kind of environmental protective type chemical raw material that meets modern times " cleaning procedure " requirement, so the synthetic technology of DMC has received the extensive attention of domestic and international chemical circles.
The initial working method of DMC is a phosgenation, promptly succeeded in developing in 1918, but the toxicity of phosgene and corrodibility has limited the application of this method, particularly receives the raising day by day of global attention degree along with environmental protection, and phosgenation is eliminated.
Early 1980s, gondola EniChem company has realized being the commercialization by the synthetic DMC technology of methanol oxidation carbonylation of catalyzer with CuCl, and this is first technology that realizes the synthetic DMC of industrialized non-phosgene, also is to use the widest technology.The deactivation phenomenom of catalyzer was serious when the defective of this technology was high conversion, so its per pass conversion is merely 20%.
U.S. Texaco company has developed elder generation and has generated NSC 11801 by oxyethane and carbon dioxide reaction; Produce the technology of DMC again through transesterify with methyl alcohol; This technology coproduction terepthaloyl moietie; Realized that in 1992 industriallization, this process quilt think that productive rate is lower, production cost is higher, had only when the DMC YO is higher than 55kt its investment and cost just can compete with additive method; Also have a kind of emerging technology in addition, promptly urea methyl alcohol is separated reaction, is a big problem but how to reduce cost.
Patent CN03119514 relates to a kind of method of direct Synthesis of dimethyl carbonate; Its step comprises: in reaction vessel, add oxirane, methyl alcohol, carbonic acid gas and catalyzer; The mol ratio of each raw material is 1: 2～10: 10～20, and the add-on of catalyzer is 2～8wt% of reaction mixture weight; Stir, be warming up to 150～170 ℃, reacted 2～6 hours, be cooled to 110～140 ℃, continue reaction 2～6 hours; Cooling removes by filter catalyzer, or adopts supercritical CO
2Extract, obtain the reaction solution of carbonated dimethyl ester.This reaction process is complicated, and the methylcarbonate selectivity is low, has only about 50% usually.
Summary of the invention
Technical problem to be solved by this invention is the low problem of methylcarbonate selectivity that in the past exists in the technology, and a kind of method of new CO coupling production methylcarbonate is provided.This method has the high advantage of methylcarbonate selectivity.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of method of CO coupling production methylcarbonate may further comprise the steps:
A) gas that contains methyl nitrite at first gets in first reaction zone with the CO raw material and contacts with palladium-containing catalyst I, generates the first strand of reaction effluent that contains unreacted methyl nitrite, CO and product methylcarbonate;
B) first strand of reaction effluent gets into gas-liquid separator;, the liquid product that gas-liquid separation obtains obtains the methylcarbonate product after getting into the subsequent separation system separation; In at least one second reaction zone of gas phase mixture entering that gas-liquid separation obtains, contact, generate the second strand of reaction effluent that contains methylcarbonate with palladium-containing catalyst II;
Wherein, the mol ratio of the first reaction zone raw material CO and methyl nitrite is 0.5～3: 1.
The first reaction zone operational condition in the technique scheme: temperature of reaction is 60～130 ℃, and reaction contact time is 0.5～6 second, and reaction pressure is 0.05～1.5MPa; The first reactor drum preferred operations condition: temperature of reaction is 70～120 ℃, and reaction contact time is 0.7～5 second, and reaction pressure is 0.08～1.0MPa.Second reactor operating condition: temperature of reaction is 70～150 ℃, and reaction contact time is 0.5～6 second, and reaction pressure is 0.05～1.5MPa; The second reactor drum preferred operations condition: temperature of reaction is 80～140 ℃, and reaction contact time is 0.7～5 second, and reaction pressure is 0.08～1.0MPa.Palladium-containing catalyst I and palladium-containing catalyst II all with at least a in silicon oxide, aluminum oxide or the molecular sieve be carrier, preferred aluminum oxide is a carrier, molecular screening is from ZSM-5, mordenite, MCM-22 or beta-molecular sieve.Active ingredient is a palladium metal, is benchmark with the carrier, and the weight content of palladium is 0.1～5%, and the preferred weight content range is 0.2～3%.
Research shows that in CO and methyl nitrite coupling reaction process, the methylcarbonate product of generation is in subsequent reactor beds process; Secondary reaction can further take place in self on the one hand; Cause reacting the purpose selectivity of product and reduce, on the other hand, the existence meeting of methylcarbonate product suppresses the reactive behavior of the transforming degree or the reduction catalyzer of raw material from the kinetics angle; Cause the raw material per pass conversion to reduce, internal circulating load strengthens.The present invention adopts at least two reactor drum polyphones, and each reaction zone elute is after gas-liquid separator carries out gas-liquid separation, and liquid phase is sent into follow-up system as thick product and further made the purpose product, and gas-phase product continues to get into subsequent reactor and reacts.Not only reduce the probability that secondary reaction further takes place the purpose product, help accelerating main reaction speed from the kinetics angle simultaneously, thereby reach the purpose that improves purpose selectivity of product and per pass conversion.
Adopt technical scheme of the present invention; At first getting into first reaction zone with CO with methyl nitrite contacts with palladium-containing catalyst I; Generate first strand of reaction effluent; The first reaction zone operational condition: temperature of reaction is 70～120 ℃, and reaction contact time is 0.7～5 second, and reaction pressure is 0.08～1.0MPa; First strand of reaction effluent gets into gas-liquid separator; The liquid product that obtains through gas-liquid separation gets into subsequent separation system to be separated the back and obtains the methylcarbonate product, through the gas phase mixture of gas-liquid separation acquisition, gets at least one second reaction zone and contacts with palladium-containing catalyst II; Generation contains second strand of reaction effluent of methylcarbonate; The second reaction zone operational condition: temperature of reaction is 80～140 ℃, and reaction contact time is 0.7～5 second, and reaction pressure is 0.08～1.0MPa.The mol ratio of the first reaction zone raw material CO and methyl nitrite is 0.5～3: 1; Palladium-containing catalyst I and palladium-containing catalyst II all are carrier with the aluminum oxide; With the carrier is benchmark, and the weight content of palladium is that the selectivity of methylcarbonate is the highest can be greater than 90% under 0.2～3% the condition; The space-time yield of methylcarbonate can obtain better technical effect greater than 400 gram/(liters per hours).
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 0.7: 1; Load palladium catalyst I and palladium catalyst II in reactor drum I and the reactor drum II respectively, wherein palladium catalyst I and palladium catalyst II are carrier with the aluminum oxide all, are benchmark with the carrier; The weight content of palladium is 1.5%; CO and methyl nitrite raw material are introduced into first reactor drum and contact with palladium catalyst I, reaction formation reaction elute I.Reaction effluent I gets into gas-liquid separator, gets into through the liquid product that gas-liquid separation obtains and obtains the methylcarbonate product after subsequent separation system is separated, through the gas phase mixture of gas-liquid separation acquisition; Get into second reactor drum and contact with palladium catalyst II, reaction formation reaction elute II, reaction effluent II obtains the methylcarbonate product after separating; Wherein, First reactor operating condition: temperature of reaction is 90 ℃, and reaction contact time is 1 second, and reaction pressure is 0.08MPa; Second reactor operating condition: temperature of reaction is 130 ℃, and reaction contact time is 3 seconds, and reaction pressure is 0.08MPa, and its reaction result is: the space-time yield of methylcarbonate is 300 gram/(liters per hours), and the selectivity of methylcarbonate is 91.2%.
[embodiment 2]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 0.8: 1; Load palladium catalyst I and palladium catalyst II in reactor drum I and the reactor drum II respectively, wherein palladium catalyst I is carrier with the silicon oxide, and palladium catalyst II is carrier with the aluminum oxide; With the carrier is benchmark, and the weight content of palladium is respectively 0.5% and 1%, CO and methyl nitrite raw material; Be introduced into first reactor drum and contact, reaction formation reaction elute I with palladium catalyst I.Reaction effluent I gets into gas-liquid separator, gets into through the liquid product that gas-liquid separation obtains and obtains the methylcarbonate product after subsequent separation system is separated, through the gas phase mixture of gas-liquid separation acquisition; Get into second reactor drum and contact with palladium catalyst II, reaction formation reaction elute II, reaction effluent II obtains the methylcarbonate product after separating; Wherein, First reactor operating condition: temperature of reaction is 100 ℃, and reaction contact time is 1 second, and reaction pressure is 0.15MPa; Second reactor operating condition: temperature of reaction is 150 ℃, and reaction contact time is 3 seconds, and reaction pressure is 0.15MPa, and its reaction result is: the space-time yield of methylcarbonate is 380 gram/(liters per hours), and the selectivity of methylcarbonate is 91.9%.
[embodiment 3]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 1: 1; Load palladium catalyst I and palladium catalyst II in reactor drum I and the reactor drum II respectively, wherein palladium catalyst I is that 150: 1 ZSM-5 molecular sieve is a carrier with the Si/Al mol ratio, and palladium catalyst II is carrier with the aluminum oxide; With the carrier is benchmark, and the weight content of palladium is respectively 0.6% and 3%, CO and methyl nitrite raw material; Be introduced into first reactor drum and contact, reaction formation reaction elute I with palladium catalyst I.Reaction effluent I gets into gas-liquid separator;, the liquid product that gas-liquid separation obtains obtains the methylcarbonate product after getting into the subsequent separation system separation; Gas phase mixture through gas-liquid separation obtains gets into second reactor drum and contacts with palladium catalyst II, and reaction formation reaction elute is 80 ℃; Reaction contact time is 3 seconds, and reaction pressure is 1.5MPa; Second reactor operating condition: temperature of reaction is 120 ℃, and reaction contact time is 4 seconds, and reaction pressure is 1.5MPa, and its reaction result is: the space-time yield of methylcarbonate is 410 gram/(liters per hours), and the selectivity of methylcarbonate is 92.1%.
[embodiment 4]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 1.6: 1; Load palladium catalyst I and palladium catalyst II in reactor drum I and the reactor drum II respectively, wherein palladium catalyst I and palladium catalyst II are carrier with the aluminum oxide all, are benchmark with the carrier; The weight content of palladium is respectively 0.8% and 1.2%; CO and methyl nitrite raw material are introduced into first reactor drum and contact with palladium catalyst I, reaction formation reaction elute I.Reaction effluent I gets into gas-liquid separator, gets into through the liquid product that gas-liquid separation obtains and obtains the methylcarbonate product after subsequent separation system is separated, through the gas phase mixture of gas-liquid separation acquisition; Get into second reactor drum and contact with palladium catalyst II, reaction formation reaction elute II, reaction effluent II obtains the methylcarbonate product after separating; Wherein, First reactor operating condition: temperature of reaction is 95 ℃, and reaction contact time is 1 second, and reaction pressure is 0.5MPa; Second reactor operating condition: temperature of reaction is 110 ℃, and reaction contact time is 4 seconds, and reaction pressure is 0.5MPa, and its reaction result is: the space-time yield of methylcarbonate is 380 gram/(liters per hours), and the selectivity of methylcarbonate is 89.8%.
[embodiment 5]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 2: 1; Load palladium catalyst I and palladium catalyst II in reactor drum I and the reactor drum II respectively, wherein palladium catalyst I and palladium catalyst II are carrier with the aluminum oxide all, are benchmark with the carrier; The weight content of palladium is respectively 0.4% and 5%; CO and methyl nitrite raw material are introduced into first reactor drum and contact with palladium catalyst I, reaction formation reaction elute I.Reaction effluent I gets into gas-liquid separator, gets into through the liquid product that gas-liquid separation obtains and obtains the methylcarbonate product after subsequent separation system is separated, through the gas phase mixture of gas-liquid separation acquisition; Get into second reactor drum and contact with palladium catalyst II, reaction formation reaction elute II, reaction effluent II obtains the methylcarbonate product after separating; Wherein, First reactor operating condition: temperature of reaction is 95 ℃, and reaction contact time is 2 seconds, and reaction pressure is 0.5MPa; Second reactor operating condition: temperature of reaction is 110 ℃, and reaction contact time is 0.5 second, and reaction pressure is 0.5MPa, and its reaction result is: the space-time yield of methylcarbonate is 430 gram/(liters per hours), and the selectivity of methylcarbonate is 92.3%.
[embodiment 6]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 3: 1; Load palladium catalyst I and palladium catalyst II in reactor drum I and the reactor drum II respectively, wherein palladium catalyst I is carrier with MCM-22, and catalyst I I is carrier with the beta-molecular sieve; With the carrier is benchmark, and the weight content of palladium is respectively 3% and 2%, CO and methyl nitrite raw material; Be introduced into first reactor drum and contact, reaction formation reaction elute I with palladium catalyst I.Reaction effluent I gets into gas-liquid separator, gets into through the liquid product that gas-liquid separation obtains and obtains the methylcarbonate product after subsequent separation system is separated, through the gas phase mixture of gas-liquid separation acquisition; Get into second reactor drum and contact with palladium catalyst II, reaction formation reaction elute II, reaction effluent II obtains the methylcarbonate product after separating; Wherein, First reactor operating condition: temperature of reaction is 80 ℃, and reaction contact time is 3 seconds, and reaction pressure is 1.5MPa; Second reactor operating condition: temperature of reaction is 120 ℃, and reaction contact time is 4 seconds, and reaction pressure is 1.5MPa, and its reaction result is: the space-time yield of methylcarbonate is 450 gram/(liters per hours), and the selectivity of methylcarbonate is 93.2%.
[embodiment 7]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 0.8: 1; Load palladium catalyst I, palladium catalyst II and palladium catalyst III in reactor drum I and reactor drum II and the reactor drum III respectively, wherein palladium catalyst I, palladium catalyst II and palladium catalyst III are carrier with the aluminum oxide all, are benchmark with the carrier; The weight content of palladium is 1.5%; CO and methyl nitrite raw material are introduced into first reactor drum and contact with palladium catalyst I, reaction formation reaction elute I.Reaction effluent I gets into gas-liquid separator I;, the liquid product that gas-liquid separation obtains obtains the methylcarbonate product I after getting into the subsequent separation system separation; Gas phase mixture I through the gas-liquid separation acquisition; Get into second reactor drum and contact with palladium catalyst II, reaction formation reaction elute II, reaction effluent II obtains methylcarbonate product I I after separating; Reaction effluent II gets into gas-liquid separator II; After the liquid product that gas-liquid separation obtains gets into the subsequent separation system separation, obtain methylcarbonate product I I, the gas phase mixture II through gas-liquid separation obtains gets into the 3rd reactor drum and contacts with palladium catalyst III; Reaction formation reaction elute III; Reaction effluent III obtains methylcarbonate product I II after separating, wherein, first reactor operating condition: temperature of reaction is 130 ℃; Reaction contact time is 1 second, and reaction pressure is 0.08MPa; The operational condition of second reactor drum and the 3rd reactor drum is: temperature of reaction is 130 ℃; Reaction contact time is 3 seconds; Reaction pressure is 0.08MPa, and its reaction result is: the space-time yield of methylcarbonate is 415 gram/(liters per hours), and the selectivity of methylcarbonate is 91.8%.
[comparative example 1]
According to [embodiment 7] identical catalyzer, condition and reaction raw materials, just only adopt a reactor drum, do not carry out gas-liquid separation, its reaction result is following: the space-time yield of methylcarbonate is 390 gram/(liters per hours), and the selectivity of methylcarbonate is 89.1%.
Claims (5)
1. the method for a CO coupling production methylcarbonate may further comprise the steps:
A) gas that contains methyl nitrite at first gets in first reaction zone with the CO raw material and contacts with palladium-containing catalyst I, generates the first strand of reaction effluent that contains unreacted methyl nitrite, CO and methylcarbonate;
B) first strand of reaction effluent gets into gas-liquid separator;, the liquid product that gas-liquid separation obtains obtains the methylcarbonate product after getting into the subsequent separation system separation; In at least one second reaction zone of gas phase mixture entering that gas-liquid separation obtains, contact, generate the second strand of reaction effluent that contains methylcarbonate with palladium-containing catalyst II;
Wherein, the mol ratio of the first reaction zone raw material CO and methyl nitrite is 0.5～3: 1.
2. according to the method for the said CO coupling production of claim 1 methylcarbonate, it is characterized in that the first reaction zone operational condition: temperature of reaction is 60～130 ℃, and reaction contact time is 0.5～6 second, and reaction pressure is 0.05～1.5MPa; The second reaction zone operational condition: temperature of reaction is 70～150 ℃, and reaction contact time is 0.5～6 second, and reaction pressure is 0.05～1.5MPa.
3. according to the method for the said CO coupling production of claim 2 methylcarbonate, it is characterized in that the first reaction zone operational condition: temperature of reaction is 70～120 ℃, and reaction contact time is 0.7～5 second, and reaction pressure is 0.08～1.0MPa; The second reaction zone operational condition: temperature of reaction is 80～140 ℃, and reaction contact time is 0.7～5 second, and reaction pressure is 0.08～1.0MPa.
4. according to the method for the said CO coupling production of claim 1 methylcarbonate; It is characterized in that palladium-containing catalyst I and palladium-containing catalyst II are carrier with at least a in silicon oxide, aluminum oxide or the molecular sieve; Active ingredient is a palladium metal; With the carrier is benchmark, and the weight percentage of palladium is 0.1～5%; Molecular screening is from ZSM-5, mordenite, MCM-22 or beta-molecular sieve.
5. according to the method for the said CO coupling production of claim 4 methylcarbonate, it is characterized in that palladium-containing catalyst I and palladium-containing catalyst II are carrier with the aluminum oxide all, is benchmark with the carrier, and the weight percentage of palladium is 0.2～3%.
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| CN2011100465503A CN102649757A (en) | 2011-02-25 | 2011-02-25 | Method for producing dimethyl carbonate through CO coupling |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956161A (en) * | 2021-11-22 | 2022-01-21 | 中国科学院宁波材料技术与工程研究所 | Method and system for continuously producing dimethyl carbonate |
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| CN1227839A (en) * | 1999-02-01 | 1999-09-08 | 天津大学 | Process for low-pressure synthesis of dimethyl carbonate by carbon monoxide |
| CN101475473A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing oxalate by coupling reaction of CO |
| CN101543784A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN101851160A (en) * | 2010-06-04 | 2010-10-06 | 天津大学 | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst |
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2011
- 2011-02-25 CN CN2011100465503A patent/CN102649757A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227839A (en) * | 1999-02-01 | 1999-09-08 | 天津大学 | Process for low-pressure synthesis of dimethyl carbonate by carbon monoxide |
| CN101475473A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing oxalate by coupling reaction of CO |
| CN101543784A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN101851160A (en) * | 2010-06-04 | 2010-10-06 | 天津大学 | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956161A (en) * | 2021-11-22 | 2022-01-21 | 中国科学院宁波材料技术与工程研究所 | Method and system for continuously producing dimethyl carbonate |
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Application publication date: 20120829 |