CN102649752A - Method for preparing dimethyl carbonate by CO coupling catalytic reaction - Google Patents
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Abstract
The invention relates to a method for preparing dimethyl carbonate by a CO coupling catalytic reaction, which mainly solves the technical problem in the prior that the product is low in selectivity. The technical scheme adopted by the invention is that under conditions that the reaction temperature is 100-180 DEG C, the volume space velocity is 500-10,000 h<-1>, and the reaction pressure is negative 0.08-1.5 MPa, raw materials are in contact with a catalyst through a mixing bed reactor filled by inactive fillers and palladium-contained catalysts, wherein the nitrous acid methyl ester and CO react in the raw materials to generate the dimethyl carbonate; and in percentage of the carrier weight, the metal palladium or an oxide thereof in the palladium-contained catalyst is 0.05-1.5 percent, and the mixed filling ratio of the inactive filler to the palladium-containing catalyst is (0.1-5):1. According to the invention, the problem is better solved, and the method is suitable for the industrial production of dimethyl carbonate.
Description
Technical field
The present invention relates to the method that a kind of CO coupling catalyzed reaction prepares methylcarbonate, particularly prepare the method for methylcarbonate about CO and methyl nitrite coupling catalyzed reaction.
Background technology
Methylcarbonate is called for short DMC, is a kind of water white transparency, slightly scent of, little sweet liquid during normal temperature, 4 ℃ of fusing points, 90.1 ℃ of boiling points, density 1.069g/cm3 is 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 CN03115329.1 relates to the preparation and the method for use thereof of a kind of mesoporous nano hydridization composite catalyst of the synthetic methylcarbonate of methanol solution phase oxidation carbonylation.Catalyzer is made up of through the hybrid mesoporous material support of the organic/inorganic nano of special processing copper halide and a kind of surface among the present invention.This carrier adopts the organic alcoxyl silane and the inorganic nanometer-sized mesoporous carrier that contain functional group to prepare through the surface graft method.But should the technology reaction pressure high, complex technical process.
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.
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, provides a kind of new CO coupling catalyzed reaction to prepare the method for 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 catalyzed reaction prepares the method for methylcarbonate; With the mixed gas that contains methyl nitrite and CO is raw material, is 100～180 ℃ in temperature of reaction, and volume space velocity is 500～10000 hours
-1Reaction pressure is under the condition of-0.08～1.5MPa; Raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and methyl nitrite and CO reaction generates methylcarbonate in the raw material, wherein; In vehicle weight percentage ratio, the palladium metal of palladium-containing catalyst or its oxide content are 0.05～1.5%; The ratio of loading in mixture of inert packing and palladium-containing catalyst is 0.1～5: 1.
Palladium-containing catalyst is a carrier with at least a in silicon oxide, aluminum oxide or the molecular sieve in the technique scheme; Preferred aluminum oxide is a carrier; In vehicle weight percentage ratio, palladium metal or its oxide content preferable range are 0.05～1.0% in the palladium-containing catalyst, and more preferably scope is 0.05～0.8%; Inert packing is preferably from inertia aluminum oxide, porcelain ball or Stainless Steel Helices, more preferably from inertia aluminum oxide or porcelain ball.
Mixed bed reactor reaction condition optimization scope is in the technique scheme: temperature of reaction is 110～160 ℃, and volume space velocity is 1000～6000 hours
-1, reaction pressure is-0.02～1.0MPa; Reaction conditions more preferably scope is: 110～150 ℃ of temperature of reaction, volume space velocity are 1500～6000 hours
-1, reaction pressure is-0.01～0.8MPa.Contain in the mixed gas feed of methyl nitrite and CO, the mol ratio of CO and methyl nitrite is 0.5～5: 1; The preferable range of the mol ratio of CO and methyl nitrite is 0.8～2: 1.The ratio that the loads in mixture preferable range of inert packing and palladium-containing catalyst is 0.2～3: 1.
Research shows that methyl nitrite is a heat-sensitive substance, especially after temperature is higher than certain temperature; Continue to raise with temperature, the decomposition meeting of methyl nitrite constantly aggravates, therefore; For the reaction of CO coupling preparing dimethyl carbonate; Control reaction hot(test)-spot temperature, for the decomposition that prevents methyl nitrite, it is extremely important to improve the purpose product selectivity.
As everyone knows, the reaction of CO coupling preparing dimethyl carbonate is a strong exothermal reaction, and dynamics research shows; The speed of reaction of CO coupling preparing dimethyl carbonate and the distribution of activity of such catalysts component are closely related, and the distribution of the active ingredient of unit carrier specific surface is high more, and its speed of reaction is fast more; Local temperature rise is high more, and therefore, it is steady how to control reaction process; Preventing that local temperature rise is too high, and then avoid a large amount of decomposition of methyl nitrite, is the key problem in technology that improves the purpose product selectivity.Adopt the mixed bed reactor drum among the present invention, in reactor drum, inert packing and catalyzer are loaded in mixture, not only can effectively reduce the concentration that active ingredient distributes in the unit volume reactor bed; Effectively avoid local reaction speed too fast; Simultaneously, the function of thermal barrier is also played in the introducing of inert packing, effectively the accelerated heat transmission; Heat dispersing; Avoid local temperature rise too high and cause the speed of reaction of CO and methyl nitrite too fast, promptly fully ensured conversion of raw material, also play the purpose of effective raising purpose selectivity of product simultaneously.Among the present invention; The mode of loading in mixture of inert packing and catalyzer can be loaded in many ways in the mixed bed reactor drum; It is big to load in mixture ratio at reactor inlet section place's inert packing and catalyzer, progressively reduces along beds then, also can evenly load in mixture etc. by whole bed.
Adopting technical scheme of the present invention, is raw material with the mixed gas that contains methyl nitrite and CO, is 100～180 ℃ in temperature of reaction, and volume space velocity is 500～10000 hours
-1Reaction pressure is under the condition of-0.08～1.5MPa; Raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and methyl nitrite and CO reaction generates methylcarbonate in the raw material, wherein; In vehicle weight percentage ratio, the palladium metal of palladium-containing catalyst or its oxide content are 0.05～1.5%; The ratio of loading in mixture of inert packing and palladium-containing catalyst is 0.1～5: 1; The mol ratio of CO and methyl nitrite is that the selectivity of methylcarbonate can obtain better technical effect greater than 90% under 0.5～5: 1 the condition in the raw material.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Using αYang Hualv to be carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 0.05% palladium catalyst, and inert packing is selected from aluminum oxide, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 0.6: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 1.2: 1, and 130 ℃ of temperature of reaction, the reaction volume air speed is 2000 hours
-1Reaction pressure is under the condition of 0.08MPa; Raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and its reaction result is: the space-time yield of methylcarbonate be 375 grams/(hour. rise), the selectivity of methylcarbonate is 92.2%.
[embodiment 2]
Using αYang Hualv to be carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 0.08% palladium catalyst, and inert packing is selected from aluminum oxide, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 0.2: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 0.8: 1, and 110 ℃ of temperature of reaction, the reaction volume air speed is 800 hours
-1Reaction pressure is-condition of 0.05MPa under, raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 408 grams/(hour. rise), the selectivity of methylcarbonate is 89.7%.
[embodiment 3]
Using αYang Hualv to be carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 0.15% palladium catalyst, and inert packing is selected from the porcelain ball, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 0.5: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 2: 1, and 140 ℃ of temperature of reaction, the reaction volume air speed is 3000 hours
-1Reaction pressure is-condition of 0.02MPa under, raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result be the space-time yield of methylcarbonate be 415 grams/(hour. rise), the selectivity of methylcarbonate is 99.1%.
[embodiment 4]
Using αYang Hualv to be carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 0.3% palladium catalyst, and inert packing is selected from aluminum oxide, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 2: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 4: 1, and 160 ℃ of temperature of reaction, the reaction volume air speed is 6000 hours
-1Reaction pressure is under the condition of 0.02MPa, and raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 418 grams/(hour. rise), the selectivity of methylcarbonate is 92.1%.
[embodiment 5]
Using silicon oxide to be carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 0.3% palladium catalyst, and inert packing is selected from stainless steel, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 1.5: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 1.3: 1, and 170 ℃ of temperature of reaction, the reaction volume air speed is 8000 hours
-1Reaction pressure is under the condition of 0.1MPa, and raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 435 grams/(hour. rise), the selectivity of methylcarbonate is 93.4%.
[embodiment 6]
Using gamma-alumina to be carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 0.5% palladium catalyst, and inert packing is selected from aluminum oxide, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 0.5: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 1.5: 1, and 130 ℃ of temperature of reaction, the reaction volume air speed is 2000 hours
-1Reaction pressure is under the condition of 0.2MPa, and raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 432 grams/(hour. rise), the selectivity of methylcarbonate is 90.7%.
[embodiment 7]
Using αYang Hualv to be carrier, is benchmark with the vehicle weight, and with the load method preparation, palladous oxide content is 0.8%; The content of zinc oxide is 0.2% palladium catalyst, and inert packing is selected from aluminum oxide, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 0.8: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 1.3: 1, and 120 ℃ of temperature of reaction, the reaction volume air speed is 1500 hours
-1Reaction pressure is under the condition of 0.3MPa, and raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 421 grams/(hour. rise), the selectivity of methylcarbonate is 92.4%.
[embodiment 8]
Using silica alumina ratio is that 600: 1 ZSM-5 molecular sieve is carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 1.2% palladium catalyst, and inert packing is selected from the porcelain ball, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 0.6: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 1.3: 1, and 130 ℃ of temperature of reaction, the reaction volume air speed is 4000 hours
-1Reaction pressure is under the condition of 0.1MPa, and raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 432 grams/(hour. rise), the selectivity of methylcarbonate is 88.1%.
[embodiment 9]
Using silicon oxide to be carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 1.4% palladium catalyst, and inert packing is selected from stainless steel, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 3: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 1.5: 1, and 120 ℃ of temperature of reaction, the reaction volume air speed is 3000 hours
-1Reaction pressure is under the condition of 0.1MPa, and raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 415 grams/(hour. rise), the selectivity of methylcarbonate is 89.7%.
[embodiment 10]
Using silica alumina ratio is that 800: 1 ZSM-5 molecular sieve is carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 0.7% palladium catalyst, and inert packing is selected from stainless steel, and the ratio of loading in mixture of inert packing and palladium-containing catalyst is 1: 1; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein; The mol ratio of CO and methyl nitrite is 1.2: 1, and 130 ℃ of temperature of reaction, the reaction volume air speed is 4000 hours
-1Reaction pressure is under the condition of 0.05MPa, and raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 395 grams/(hour. rise), the selectivity of methylcarbonate is 91.6%.
[embodiment 11]
Using αYang Hualv to be carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 0.6% palladium catalyst, and inert packing is selected from αYang Hualv, and the ratio of loading in mixture that inert packing and palladium-containing catalyst are highly located to reactor drum 1/2 at reactor inlet is 2: 1; The ratio of loading in mixture of highly locating reactor exit at reactor drum 1/2 is 1: 1, catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite; Wherein, The mol ratio of CO and methyl nitrite is 0.8: 1, and 130 ℃ of temperature of reaction, the reaction volume air speed is 4000 hours
-1Reaction pressure is under the condition of 0.05MPa, and raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 402 grams/(hour. rise), the selectivity of methylcarbonate is 94.1%.
[embodiment 12]
Using gamma-alumina to be carrier, is benchmark with the vehicle weight, prepares with load method; Palladous oxide content is 0.6% palladium catalyst, and inert packing is selected from αYang Hualv, and inert packing and palladium-containing catalyst are to successively decrease gradually by 3: 1～0.5: 1 to load at reactor inlet to the ratio of loading in mixture of reactor exit; Catalyzer before use through 300 ℃ of excess temperatures with hydrogen reducing 4 hours; With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 0.6: 1; 130 ℃ of temperature of reaction, the reaction volume air speed is 4000 hours
-1Reaction pressure is under the condition of 0.05MPa, and raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and reacts; Its reaction result is: the space-time yield of methylcarbonate be 381 grams/(hour. rise), the selectivity of methylcarbonate is 92.0%.
[comparative example 1]
According to embodiment 7 same reaction conditions and reaction raw materials, only adopt palladium-containing catalyst, dilute without inert packing; With CO and methyl nitrite is raw material, and wherein, the mol ratio of CO and methyl nitrite is 1.3: 1; 120 ℃ of temperature of reaction, the reaction volume air speed is 1500 hours
-1, reaction pressure is under the condition of 0.3MPa, raw material contacts with catalyzer, reacts, its reaction result is: the space-time yield of methylcarbonate be 380 grams/(hour. rise), the selectivity of methylcarbonate is 82.1%.
Claims (8)
1. a CO coupling catalyzed reaction prepares the method for methylcarbonate, is raw material with the mixed gas that contains methyl nitrite and CO, is 100～180 ℃ in temperature of reaction, and volume space velocity is 500～10000 hours
-1Reaction pressure is under the condition of-0.08～1.5MPa; Raw material contacts with catalyzer through the mixed bed reactor drum that inert packing and palladium-containing catalyst are housed, and methyl nitrite and CO reaction generates methylcarbonate in the raw material, wherein; In vehicle weight percentage ratio, the palladium metal of palladium-containing catalyst or its oxide content are 0.05～1.5%; The weight ratio of loading in mixture of inert packing and palladium-containing catalyst is 0.1～5: 1.
2. the method for preparing methylcarbonate according to the said CO coupling of claim 1 catalyzed 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; In vehicle weight percentage ratio; Palladium metal or its oxide content are 0.05～1.0% in the palladium-containing catalyst, and inert packing is selected from inertia aluminum oxide, porcelain ball or Stainless Steel Helices.
3. prepare the method for methylcarbonate according to the said CO coupling of claim 2 catalyzed reaction, it is characterized in that the carrier of palladium-containing catalyst all is selected from aluminum oxide; In vehicle weight percentage ratio, palladium metal or its oxide content are 0.05～0.8% in the palladium-containing catalyst, and inert packing is selected from inertia aluminum oxide or porcelain ball.
4. the method for preparing methylcarbonate according to the said CO coupling of claim 1 catalyzed reaction is characterized in that mixed bed reactor reaction temperature is 110～160 ℃, and volume space velocity is 1000～6000 hours
-1, reaction pressure is-0.02～1.0MPa.
5. the method for preparing methylcarbonate according to the said CO coupling of claim 4 catalyzed reaction is characterized in that mixed bed reactor reaction temperature is 110～150 ℃, and volume space velocity is 1500～6000 hours
-1, reaction pressure is-0.01～0.8MPa.
6. prepare the method for methylcarbonate according to the said CO coupling of claim 1 catalyzed reaction, it is characterized in that containing in the mixed gas feed of methyl nitrite and CO, the mol ratio of CO and methyl nitrite is 0.5～5: 1.
7. prepare the method for methylcarbonate according to the said CO coupling of claim 6 catalyzed reaction, it is characterized in that containing in the mixed gas feed of methyl nitrite and CO, the mol ratio of CO and methyl nitrite is 0.8～2: 1.
8. prepare the method for methylcarbonate according to the said CO coupling of claim 1 catalyzed reaction, the ratio of loading in mixture that it is characterized in that inert packing and palladium-containing catalyst is 0.2～3: 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108218705A (en) * | 2018-01-25 | 2018-06-29 | 宁波中科远东催化工程技术有限公司 | A kind of method of CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108218705A (en) * | 2018-01-25 | 2018-06-29 | 宁波中科远东催化工程技术有限公司 | A kind of method of CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method |
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Application publication date: 20120829 |