CN102649756A - Method for producing dimethyl carbonate through CO coupling gas phase reaction - Google Patents
Method for producing dimethyl carbonate through CO coupling gas phase reaction Download PDFInfo
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- CN102649756A CN102649756A CN2011100465359A CN201110046535A CN102649756A CN 102649756 A CN102649756 A CN 102649756A CN 2011100465359 A CN2011100465359 A CN 2011100465359A CN 201110046535 A CN201110046535 A CN 201110046535A CN 102649756 A CN102649756 A CN 102649756A
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Abstract
The invention relates to a method for producing dimethyl carbonate through CO coupling gas phase reaction, and mainly solves the technical problem of low selectivity of a target product existing in the prior art. According to the method, a raw material mixture containing methyl nitrite and CO is contacted with a palladium-containing catalyst under the conditions of reaction temperature of 80-160 DEG C and reaction pressure of -0.09 to 1.5 MPa to produce a reaction effluent containing the dimethyl carbonate, wherein the palladium-containing catalyst is fixed on a rotor of a rotating packed bed reactor; and the molar ratio of the CO to the methyl nitrite in the raw material is 1-5:1. 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 CO coupling gas-phase reaction and produce the method for 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 CN 03119514 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.
The EP0023745A3 patent that Britain Imperial Chemical Industries (ICI) propose is mentioned rotating bed and can be used for processes such as absorption, parsing, distillation, but does not disclose the utilisation technology of industrially scalable.CN1064338A discloses the method for utilizing rotating bed to carry out the oil-field flooding deoxidation; CN1116146A discloses a kind of method that under super gravity field, prepares ultrafine particle.
The super gravity field technology is the new technology that early eighties just occurs; Its internal mechanism is also continuing exploration; Research for application and development is still constantly being carried out, and new Application Areas also is not applied to the report that CO coupling preparing dimethyl carbonate is produced about rotating bed for now also in continuous developing.
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 document, the method that provides a kind of new CO coupling gas-phase reaction to produce methylcarbonate.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 CO coupling gas-phase reaction is produced the method for methylcarbonate; The raw mix that contains methyl nitrite and CO, 80～160 ℃ of temperature of reaction, reaction pressure is to contact with palladium-containing catalyst under the condition of-0.09～1.5MPa; Generation contains the reaction effluent of methylcarbonate, it is characterized in that palladium-containing catalyst is fixed on the rotor of rotating packed bed reactor;
Wherein, the mol ratio of CO and methyl nitrite is 0.5～5: 1 in the raw material.
The preferred reaction conditions of rotating packed bed reactor is in the technique scheme: 90～150 ℃ of temperature of reaction, reaction pressure are-0.05～1.0MPa; The rotating speed preferable range of the rotor of rotating packed bed reactor is 100～5000rpm.The more preferably reaction conditions of rotating packed bed reactor is: 100～150 ℃ of temperature of reaction, reaction pressure are 0.01～1.0MPa; The rotating speed of the rotor of rotating packed bed reactor more preferably scope is 600～4000rpm.The preferable range of the mol ratio of CO and methyl nitrite is 0.5～3: 1 in the raw material.
In the technique scheme palladium-containing catalyst 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%.
As everyone knows; All materials are all attracted by the earth because of gravity on the earth; Super gravity field is the environment more much bigger than earth gravity intensity of field, and material suffered power under super gravity field is called hypergravity, utilizes hypergravity the principles of science and the practical technique that produces is called high-gravity technology.
High-gravity technology is a new technology of strengthening polyphasic flow transmission and reaction process; Since eighties of last century is come out; At home and abroad receive widely and paying attention to; Because its broad applicability and have that the volume that legacy equipment do not have is little, in light weight, energy consumption is low, easy running, easy-maintaining, safety, advantage such as can conform reliably, flexibly and more, make high-gravity technology in industrial circles such as environmental protection and material biochemical industry, wide commercial applications prospect arranged.But high-gravity technology also mainly is in the application and development stage at present, embodies a concentrated reflection of two aspects of gas-solid fluidization technology of hypergravity and hypergravity gas-liquid mass transferring technology.
The rotating bed super gravity field device, as the equipment that produces super gravity field, it is made up of gas and liquid inlet tube, rotor, gas and liquid exit usually.Its principle of work is that gas phase is introduced the rotor exocoel through gas inlet tube by the tangential, under the effect of gaseous tension, gets into filler by rotor outer rim place.Liquid is introduced rotor internal cavity by liquid inlet tube, through the shower nozzle sprinkle on the rotor inner edge.The liquid that gets into rotor receives the effect of filler in the rotor, and circumferential speed increases, and the cf-that is produced pushes it against the rotor outer rim.In this process, liquid is by fillers dispersed, the broken surface-area that forms greatly, brings in constant renewal in, and the zigzag runner has aggravated the renewal of fluid surface.Like this, fabulous mass transfer and reaction conditions have been formed at internal rotor.Liquid is thrown by rotor that shell compiles after liquid outlet tube leaves overweight machine.Gas leaves rotor from rotor center, is drawn by gas outlet tube, accomplishes mass transfer and reaction process.
Research shows that CO and methyl nitrite linked reaction are fast responses, in reaction process; The methylcarbonate product that generates is in subsequent reactor beds process, and self can secondary reaction take place further on the one hand, causes reacting the purpose selectivity of product and reduces; On the other hand; The existence meeting of methylcarbonate product causes the raw material per pass conversion to reduce from the reactive behavior of the transforming degree or the reduction catalyzer of kinetics angle inhibition raw material, and internal circulating load strengthens.Among the present invention: adopt rotating packed bed reactor; Raw material is contacted with catalyzer by rotating packed bed reactor center entering reactor drum and carries out rapid reaction; Like this; 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.
As everyone knows; The reaction of CO coupling preparing dimethyl carbonate is thermopositive reaction; Big quantity research shows; Be used for CO coupling preparing dimethyl carbonate catalyst for reaction because the concentrated heat release of coupling reaction process can cause the higher temperature rise of catalyzer, especially the temperature of catalyst active center possibly exceed catalyzer apparent temperature tens degree even more than 100 ℃, and too high local temperature rise is disadvantageous to the selectivity that improves methylcarbonate.The rotating packed bed reactor that adopts among the present invention all has favourable effect for the uniform distribution and the shifting out fast of heat of heat.
Adopting technical scheme of the present invention, is catalyzer with palladium load aluminum oxide, is benchmark with the carrier; The weight content of palladium is 0.2～3%; With the mol ratio of CO and methyl nitrite is that 0.5～3: 1 mixture is a raw material, and 100～150 ℃ of temperature of reaction, reaction pressure is 0.01～1.0MPa; The rotating speed of the rotor of rotating packed bed reactor is under the condition of 600～4000rpm; The space-time yield of methylcarbonate can be greater than 400 gram/(hours rise), and the selectivity of methylcarbonate can obtain better technical effect greater than 90%.
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 0.6: 1; Load the catalyzer of palladium load aluminum oxide in the rotating packed bed reactor (adopt the rotating packed bed reactor among the document CN02151624, catalyzer is fixed on the rotation filler, below identical); With the carrier is benchmark, and the weight content of palladium is 1.5%, and CO gets into rotary drill reactor with the methyl nitrite raw material and contacts with catalyzer; 100 ℃ of temperature of reaction, reaction pressure is-0.01MPa; The rotating speed of the rotor of rotating packed bed reactor is under the 1000rpm condition, and its reaction result is: the space-time yield of methylcarbonate is 350 gram/(hours rise), 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 the catalyzer of palladium load aluminum oxide in the rotating packed bed reactor; With the carrier is benchmark, and the weight content of palladium is 0.5%, and CO gets into rotary drill reactor with the methyl nitrite raw material and contacts with catalyzer; 150 ℃ of temperature of reaction, reaction pressure is-0.06MPa; The rotating speed of the rotor of rotating packed bed reactor is under the 2000rpm condition, and its reaction result is: the space-time yield of methylcarbonate is 380 gram/(hours rise), and the selectivity of methylcarbonate is 92.1%.
[embodiment 3]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 1: 1; Load the catalyzer (the Si/Al mol ratio is 150: 1) of palladium load ZSM-5 molecular sieve in the rotating packed bed reactor; With the carrier is benchmark, and the weight content of palladium is 0.8%, and CO gets into rotary drill reactor with the methyl nitrite raw material and contacts with catalyzer; 120 ℃ of temperature of reaction, reaction pressure is-0.02MPa; The rotating speed of the rotor of rotating packed bed reactor is under the 5000rpm condition, and its reaction result is: the space-time yield of methylcarbonate is 402 gram/(hours rise), and the selectivity of methylcarbonate is 90.1%.
[embodiment 4]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 0.8: 1; Load the catalyzer of palladium load aluminum oxide in the rotating packed bed reactor; With the carrier is benchmark, and the weight content of palladium is 0.2%, and CO gets into rotary drill reactor with the methyl nitrite raw material and contacts with catalyzer; 110 ℃ of temperature of reaction, reaction pressure is 0.05MPa; The rotating speed of the rotor of rotating packed bed reactor is under the 3000rpm condition, and its reaction result is: the space-time yield of methylcarbonate is 420 gram/(hours rise), and the selectivity of methylcarbonate is 93.8%.
[embodiment 5]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 1.2: 1; Load the catalyzer of palladium load aluminum oxide in the rotating packed bed reactor; With the carrier is benchmark, and the weight content of palladium is 0.4%, and CO gets into rotary drill reactor with the methyl nitrite raw material and contacts with catalyzer; 130 ℃ of temperature of reaction, reaction pressure is 0.2MPa; The rotating speed of the rotor of rotating packed bed reactor is under the 1000rpm condition, and its reaction result is: the space-time yield of methylcarbonate is 430 gram/(hours rise), and the selectivity of methylcarbonate is 95.3%.
[embodiment 6]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 3: 1; Load the catalyzer of palladium load MCM-22 molecular sieve in the rotating packed bed reactor; With the carrier is benchmark, and the weight content of palladium is 0.2%, and CO gets into rotary drill reactor with the methyl nitrite raw material and contacts with catalyzer; 130 ℃ of temperature of reaction, reaction pressure is 1.2MPa; The rotating speed of the rotor of rotating packed bed reactor is under the 500rpm condition, and its reaction result is: the space-time yield of methylcarbonate is 408 gram/(hours rise), and the selectivity of methylcarbonate is 92.2%.
[embodiment 7]
With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 0.7: 1; Load the catalyzer of palladium load aluminum oxide in the rotating packed bed reactor; With the carrier is benchmark, and the weight content of palladium is 0.4%, and CO gets into rotary drill reactor with the methyl nitrite raw material and contacts with catalyzer; 150 ℃ of temperature of reaction, reaction pressure is 0.3MPa; The rotating speed of the rotor of rotating packed bed reactor is under the 1500rpm condition, and its reaction result is: the space-time yield of methylcarbonate is 412 gram/(hours rise), and the selectivity of methylcarbonate is 93.1%.
[comparative example 1]
According to embodiment 7 identical catalyzer, condition and reaction raw materials, just only adopt fixed-bed reactor, its reaction result is following: the space-time yield of methylcarbonate is 401 grams/(hour rise), and the selectivity of methylcarbonate is 91.2%.
Claims (7)
1. a CO coupling gas-phase reaction is produced the method for methylcarbonate; The raw mix that contains methyl nitrite and CO; 80～160 ℃ of temperature of reaction; Reaction pressure is to contact with palladium-containing catalyst under the condition of-0.09～1.5MPa, generates the reaction effluent that contains methylcarbonate, it is characterized in that palladium-containing catalyst is fixed on the rotor of rotating packed bed reactor;
Wherein, the mol ratio of CO and methyl nitrite is 0.5～5: 1 in the raw material.
2. produce the method for methylcarbonate according to the said CO coupling of claim 1 gas-phase reaction, it is characterized in that 90～150 ℃ of the temperature of reaction of rotating packed bed reactor, reaction pressure is-0.05～1.0MPa; The rotating speed of the rotor of rotating packed bed reactor is 100～5000rpm.
3. produce the method for methylcarbonate according to the said CO coupling of claim 2 gas-phase reaction, it is characterized in that 100～150 ℃ of the temperature of reaction of rotating packed bed reactor, reaction pressure is 0.01～1.0MPa; The rotating speed of the rotor of rotating packed bed reactor is 600～4000rpm.
4. produce the method for methylcarbonate according to the said CO coupling of claim 1 gas-phase reaction; It is characterized in that palladium-containing catalyst is a carrier with at least a in silicon oxide, aluminum oxide or the molecular sieve; Active ingredient is a palladium metal, is benchmark with the carrier, and the weight percentage of palladium is 0.1～5%; Molecular screening is from ZSM-5, mordenite, MCM-22 or beta-molecular sieve.
5. producing the method for methylcarbonate according to the said CO coupling of claim 4 gas-phase reaction, it is characterized in that palladium-containing catalyst is a carrier with the aluminum oxide, is benchmark with the carrier, and the weight percentage of palladium is 0.2～3%.
6. produce the method for methylcarbonate according to the said CO coupling of claim 1 gas-phase reaction, it is characterized in that methyl nitrite is selected from methyl nitrite or methyl nitrite.
7. produce the method for methylcarbonate according to the said CO coupling of claim 1 gas-phase reaction, it is characterized in that the mol ratio of CO and methyl nitrite is 0.5～3: 1 in the raw material.
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| CN2011100465359A CN102649756A (en) | 2011-02-25 | 2011-02-25 | Method for producing dimethyl carbonate through CO coupling gas phase reaction |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103862A (en) * | 1993-07-15 | 1995-06-21 | 拜尔公司 | Process for the preparation of dimethyl carbonate |
| CN1104206A (en) * | 1993-07-15 | 1995-06-28 | 拜尔公司 | Process for the preparation of dialkyl carbonates |
| CN1227839A (en) * | 1999-02-01 | 1999-09-08 | 天津大学 | Process for low-pressure synthesis of dimethyl carbonate by carbon monoxide |
| CN1507940A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Catalytic reaction method |
| CN102219675A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for producing oxalic ester by CO coupling |
-
2011
- 2011-02-25 CN CN2011100465359A patent/CN102649756A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103862A (en) * | 1993-07-15 | 1995-06-21 | 拜尔公司 | Process for the preparation of dimethyl carbonate |
| CN1104206A (en) * | 1993-07-15 | 1995-06-28 | 拜尔公司 | Process for the preparation of dialkyl carbonates |
| CN1227839A (en) * | 1999-02-01 | 1999-09-08 | 天津大学 | Process for low-pressure synthesis of dimethyl carbonate by carbon monoxide |
| CN1507940A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Catalytic reaction method |
| CN102219675A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for producing oxalic ester by CO coupling |
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Application publication date: 20120829 |