CN102219676B - Method for preparing oxalate by CO coupling - Google Patents
Method for preparing oxalate by CO coupling Download PDFInfo
- Publication number
- CN102219676B CN102219676B CN2010101468966A CN201010146896A CN102219676B CN 102219676 B CN102219676 B CN 102219676B CN 2010101468966 A CN2010101468966 A CN 2010101468966A CN 201010146896 A CN201010146896 A CN 201010146896A CN 102219676 B CN102219676 B CN 102219676B
- Authority
- CN
- China
- Prior art keywords
- reaction
- effluent
- palladium
- reaction zone
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a method for preparing oxalate by CO coupling, and mainly solves the technical problems of low target product selectivity and low single-pass conversion in the prior art. The technical scheme of the invention comprises the following steps: (a) firstly allowing nitrite-containing gas and CO raw material to contact a palladium-containing catalyst I in a first reaction zone to generate a reaction effluent I which contains NO, oxalate, and unreacted CO; (b) allowing the reaction effluent I to react with C1-C4 alkyl alcohol and oxygen in a second reaction zone to generate a reaction effluent II, performing gas-liquid separation of the reaction effluent II in a gas-liquid separator to obtain a liquid-phase effluent III and a gas-phase effluent IV; (c) allowing the gas-phase effluent IV to contact a palladium-containing catalyst II in a third reaction zone to generate a reaction effluent V which contains oxalate. The technical scheme solves the problems well, and themethod is applicable to the industrial production of oxalate yield increase.
Description
Technical field
The present invention relates to a kind of method of CO coupling producing oxalic ester, particularly about the method for CO and methyl nitrite or ethyl nitrite coupling dimethyl oxalate processed or oxalic acid diethyl ester.
Background technology
Barkite is important Organic Chemicals, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate.Enter 21 century, barkite is subjected to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the barkite ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia solution can get high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the barkite low-voltage hydrogenation can prepare very important chemical material ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import ethylene glycol every year, and import volume was nearly 4,800,000 tons in 2007.
The production route of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, production technique cost height, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.For many years, people are seeking an operational path that cost is low, environment is good always.The sixties in last century, the D.F.Fenton of U.S. Associated Oil Company finds, carbon monoxide, pure and mild oxygen can pass through the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and U.S. ARCO company have carried out research and development in succession in this field since then.
Divide from development course for carbon monoxide oxidative coupling method synthesis of oxalate and can be divided into liquid phase method and vapor phase process.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is relatively harsher, and reaction is under high pressure carried out, the liquid-phase system corrosive equipment, and catalyzer easily runs off in the reaction process.The tool advantage of the vapor phase process of CO coupling producing oxalic ester, external company of Ube Industries Ltd. and Italian Montedisons SPA carried out vapor phase process research in succession in 1978.Wherein, the synthesis of oxalic ester by gaseous catalysis technology of emerging product company of space portion exploitation, reaction pressure 0.5MP, temperature is 80 ℃～150 ℃.
Along with carbon monoxide oxidative coupling legal system in the world is equipped with the research and development of barkite Technology, domestic many research institutions have also carried out research work to this field.According to the china natural resources characteristic distributions, be the feedstock production organic oxygen-containing compound with the carbon monoxide, for the pressure of alleviating petroleum products, rationally utilize coal and natural gas source to have very important strategic meaning.At present, to become important research project in domestic one-carbon chemical and the organic chemical industry field, successively there are how tame research institution and research institutions to be devoted to catalyzer development, process exploitation and the engineering amplification work in this field by carbon monoxide oxidative coupling method synthesis of oxalate.
Although above-mentioned numerous research institution has obtained technically than much progress, technology itself still remains further to be improved and development, especially improves reaction preference how, and aspects such as raising activity of such catalysts all need further research and break through.
Document CN200710060003.4 discloses a kind of method of CO preparing diethyl oxalate by coupling, adopt vapor phase process, CO is under the participation of ethyl nitrite, under the catalysis of bimetal loaded catalyst, coupling generates the oxalic acid diethyl ester crude product, reaction is self-enclosed working cycle, CO gas enters coupler reactor with ethyl nitrite from regeneration reactor through mixing preheating, reaction back gas is through condensation separation, obtain water white oxalic acid diethyl ester lime set, the non-condensable gas that contains NO enters regeneration reactor, in regeneration reactor and ethanol, the recirculation of oxygen reaction generation ethyl nitrite is returned coupler reactor and is used continuously, and the present invention is on the basis of lab scale research in early stage, is that background is carried out with the industrial production, running examination is continuously amplified in mould examination and the pilot scale finished under the industrial operation condition, the linked reaction temperature is low, and product concentration improves, and present method is more energy-conservation, pollution-free, high efficiency.But the per pass conversion of this technology CO is 20～60%, and the purpose selectivity of product all remains further to be improved about 96%.
Document CN 95116136.9 discloses the catalyzer of the synthetic usefulness of a kind of barkite, selects for use Z r to make auxiliary agent, develops novel Pd-Zr/Al with pickling process
2O
3Catalyzer.This catalyzer is to adopt fixed-bed reactor as carbon monoxide and the reaction of nitrous acid fat synthesis of oxalic ester by gaseous catalysis.But the yield of its barkite of catalyzer that adopts in this patent is lower, and the impurity of unstripped gas is had relatively high expectations, and the selectivity of product barkite is 95%, and the per pass conversion of nitrous acid ester is up to 64%, all remains further to be improved.
Summary of the invention
Technical problem to be solved by this invention is that the barkite selectivity that in the past exists in the document is low, and the problem that the raw material per pass conversion is low provides a kind of method of new CO coupling producing oxalic ester.This method has barkite selectivity height, the advantage that the per pass conversion of raw material is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of CO coupling producing oxalic ester may further comprise the steps:
A) gas that contains nitrous acid ester at first enters in first reaction zone with the CO raw material and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, barkite and unreacted CO;
B) alkyl alcohol of reaction effluent I and C1～C4 and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II enters gas-liquid separator, obtains liquid phase effluent III and gas phase effluent IV through gas-liquid separation;
C) gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite;
D) liquid phase effluent III obtains the barkite product with reaction effluent V after separating;
Wherein, the mol ratio of the first reaction zone raw material CO and nitrous acid ester is 1.1～5: 1.
The mol ratio of first reaction zone operational condition: the CO and nitrous acid ester is 1.1～3: 1 in the technique scheme, 100～170 ℃ of temperature of reaction, and reaction velocity is 500～6000 hours
-1, reaction pressure is 0.01～1.5MPa; The first reactor preferred operations condition: the mol ratio of CO and nitrous acid ester is 1.1～2: 1, and temperature of reaction is 110～160 ℃, and reaction velocity is 1000～5000 hours
-1, reaction pressure is 0.01～1.0MPa.The second reaction zone operational condition: the mol ratio of alkyl alcohol, NO and the oxygen of the C1～C4 of reactor inlet place is 1～30: 1: 0.1～0.25, and temperature of reaction is 20～90 ℃, and reaction contact time is 0.5～70 second, and reaction pressure is-0.05～1.0MPa; The second reaction zone preferred operations condition: the mol ratio of alkyl alcohol, NO and the oxygen of the C1～C4 of reactor inlet place is 1.5～20: 1: 0.1～0.20, and 20～70 ℃ of temperature of reaction, reaction contact time is 0.5～50 second, reaction pressure is-0.05～0.8MPa.The 3rd reaction zone operational condition: 100～170 ℃ of temperature of reaction, reaction velocity are 500～6000 hours
-1, reaction pressure is 0.02～1.5MPa; The 3rd reaction zone preferred operations condition: 110～160 ℃ of temperature of reaction, reaction velocity are 1000～5000 hours
-1, reaction pressure is 0.02～1.0MPa.
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 carrier.Active ingredient is palladium metal, is benchmark with the vehicle weight, and the weight percentage of palladium is 0.1～5%, and preferred weight percentage composition scope is 0.1～3%, and nitrous acid ester is selected from methyl nitrite or ethyl nitrite.The alkyl alcohol of C1～C4 is preferably from methyl alcohol or ethanol.
Studies show that, in CO and nitrous acid ester coupling reaction process, the NO that generates and barkite product are in subsequent reactor beds process, secondary reaction can further take place in barkite self on the one hand, cause reacting the purpose selectivity of product and reduce, on the other hand, the existence meeting of NO and barkite product suppresses the reactive behavior of 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.Among the present invention: adopt NO and C1～C4 alkyl alcohol and oxygen direct reaction generation nitrous acid ester in each reaction zone effluent, and nitrous acid ester is reaction raw materials, after separator separates, liquid phase is sent into follow-up system as thick product and is further made the purpose product, and gas-phase product continues to enter subsequent reactor and reacts.Not only reduce the probability that secondary reaction further takes place the purpose product, be conducive to accelerate 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 producing oxalic ester is thermopositive reaction, studies show that in a large number, being used for CO coupling producing oxalic ester catalyst for reaction inactivation one of the main reasons is catalyst activity component grain growth sintering, and the concentrated heat release of coupling reaction process can cause the higher temperature rise of catalyzer, especially the temperature of catalyst active center may exceed catalyzer apparent temperature tens degree even more than 100 ℃, and too high local temperature rise is very fatal to the influence of catalyst life, especially can accelerate growing up of crystal grain greatly, thus the inactivation of accelerator activator.First strand of reaction effluent plays favourable effect through the sepn process of separator to the reaction process temperature optimization among the present invention.
Adopting technical scheme of the present invention, is raw material with CO and nitrous acid ester, and raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, barkite and unreacted CO; The alkyl alcohol of reaction effluent I and C1～C4 and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the barkite product with reaction effluent V after separating; The first reaction zone operational condition wherein: temperature of reaction is 110～160 ℃, and reaction velocity is 1000～5000 hours
-1, reaction pressure is 0.05～1.0MPa; The second reaction zone operational condition: the mol ratio of alkyl alcohol, NO and the oxygen of the C1～C4 of reactor inlet place is 1.5～20: 1: 0.1～0.20, and 20～70 ℃ of temperature of reaction, reaction contact time is 0.5～50 second, reaction pressure is-0.05～0.8MPa.The 3rd reaction zone operational condition: 110～160 ℃ of temperature of reaction, reaction velocity are 1000～5000 hours
-1, reaction pressure is 0.05～1.0MPa.The mol ratio of the first reaction zone raw material CO and nitrous acid ester is 1.1～3: 1; Palladium-containing catalyst I and palladium-containing catalyst II all are carrier with the aluminum oxide, be benchmark with the vehicle weight, the weight content of palladium metal is that the CO per pass conversion is the highest can be greater than 71% under 0.1～3% the condition, the selectivity of barkite is the highest can to have obtained better technical effect greater than 99%.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Be raw material with CO and methyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I is carrier with the αYang Hualv, palladium catalyst II is carrier with the αYang Hualv also, is benchmark with the vehicle weight, and the weight content of palladium metal is respectively 0.5% and 1%, raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, dimethyl oxalate and unreacted CO; Reaction effluent I and methyl alcohol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the dimethyl oxalate product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and methyl nitrite is 2: 1, and temperature of reaction is 120 ℃, and reaction velocity is 1000 hours
-1, reaction pressure is 0.05MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place methyl alcohol, NO and oxygen is 2: 1: 0.15,30 ℃ of temperature of reaction, and reaction contact time is 2 seconds, reaction pressure is-0.05MPa.The 3rd reaction zone operational condition: 130 ℃ of temperature of reaction, reaction velocity are 2000 hours
-1, reaction pressure is 0.05MPa.Its reaction result is: CO per pass conversion 66.3%, the selectivity of dimethyl oxalate are 98.9%.
[embodiment 2]
Be raw material with CO and methyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I is carrier with the silicon oxide, palladium catalyst II is carrier with the aluminum oxide, is benchmark with the vehicle weight, and the weight content of palladium metal is respectively 0.2% and 0.8%, raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, dimethyl oxalate and unreacted CO; Reaction effluent I and methyl alcohol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the dimethyl oxalate product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and methyl nitrite is 1.5: 1, and temperature of reaction is 140 ℃, and reaction velocity is 2000 hours
-1, reaction pressure is 0.02MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place methyl alcohol, NO and oxygen is 5: 1: 0.18,70 ℃ of temperature of reaction, and reaction contact time is 8 seconds, reaction pressure is-0.02MPa.The 3rd reaction zone operational condition: 150 ℃ of temperature of reaction, reaction velocity are 5000 hours
-1, reaction pressure is 0.02MPa.Its reaction result is: CO per pass conversion 83.4%, the selectivity of dimethyl oxalate are 99.3%.
[embodiment 3]
Be raw material with CO and methyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I is carrier with ZSM-5 molecular sieve (silica alumina ratio 800: 1), palladium catalyst II is carrier with the αYang Hualv, is benchmark with the vehicle weight, and the weight content of palladium metal is respectively 0.3% and 1.5%, raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, dimethyl oxalate and unreacted CO; Reaction effluent I and methyl alcohol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the dimethyl oxalate product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and methyl nitrite is 3: 1, and temperature of reaction is 160 ℃, and reaction velocity is 5000 hours
-1, reaction pressure is 0.1MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place methyl alcohol, NO and oxygen is 20: 1: 0.24,50 ℃ of temperature of reaction, and reaction contact time is 60 seconds, reaction pressure is 0.02MPa.The 3rd reaction zone operational condition: 140 ℃ of temperature of reaction, reaction velocity are 3000 hours
-1, reaction pressure is 0.3MPa.Its reaction result is: CO per pass conversion 51.4%, the selectivity of dimethyl oxalate are 99.5%.
[embodiment 4]
Be raw material with CO and ethyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I and palladium catalyst II all are carrier with the αYang Hualv, be benchmark with the vehicle weight, the weight content of palladium metal is respectively 0.5% and 1%, and raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, oxalic acid diethyl ester and unreacted CO; Reaction effluent I and ethanol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the oxalic acid diethyl ester product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and ethyl nitrite is 1.6: 1, and temperature of reaction is 150 ℃, and reaction velocity is 4000 hours
-1, reaction pressure is 0.5MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place ethanol, NO and oxygen is 6: 1: 0.21,30 ℃ of temperature of reaction, and reaction contact time is 40 seconds, reaction pressure is 0.5MPa.The 3rd reaction zone operational condition: 130 ℃ of temperature of reaction, reaction velocity are 2000 hours
-1, reaction pressure is 0.8MPa.Its reaction result is: CO per pass conversion 84.4%, the selectivity of oxalic acid diethyl ester are 98.8%.
[embodiment 5]
Be raw material with CO and ethyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I and palladium catalyst II all are carrier with the αYang Hualv, palladium catalyst II is carrier with the gama-alumina, is benchmark with the vehicle weight, and the weight content of palladium metal is respectively 0.8% and 0.2%, raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, oxalic acid diethyl ester and unreacted CO; Reaction effluent I and ethanol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the oxalic acid diethyl ester product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and ethyl nitrite is 1.3: 1, and temperature of reaction is 120 ℃, and reaction velocity is 4500 hours
-1, reaction pressure is 0.8MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place ethanol, NO and oxygen is 6: 1: 0.10,20 ℃ of temperature of reaction, and reaction contact time is 60 seconds, reaction pressure is 0.1MPa.The 3rd reaction zone operational condition: 155 ℃ of temperature of reaction, reaction velocity are 4000 hours
-1, reaction pressure is 1.2MPa.Its reaction result is: CO per pass conversion 86.4%, the selectivity of oxalic acid diethyl ester are 99.1%.
[embodiment 6]
Be raw material with CO and propyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I is carrier with the αYang Hualv, palladium catalyst II also is carrier with the αYang Hualv, be benchmark with the vehicle weight, the weight content of palladium metal is respectively 0.2% and 0.4%, palladium catalyst I also contains 0.3% cerium, raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, dipropyl oxalate and unreacted CO; Reaction effluent I and propyl alcohol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the dipropyl oxalate product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and propyl nitrite is 1.5: 1, and temperature of reaction is 130 ℃, and reaction velocity is 3000 hours
-1, reaction pressure is 0.3MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place propyl alcohol, NO and oxygen is 2: 1: 0.20,35 ℃ of temperature of reaction, and reaction contact time is 15 seconds, reaction pressure is 0.1MPa.The 3rd reaction zone operational condition: 140 ℃ of temperature of reaction, reaction velocity are 1500 hours
-1, reaction pressure is 0.5MPa.Its reaction result is: CO per pass conversion 81.4%, the selectivity of dipropyl oxalate are 98.2%.
[embodiment 7]
Be raw material with CO and methyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I is carrier with the αYang Hualv, palladium catalyst II also is carrier with the αYang Hualv, be benchmark with the vehicle weight, the weight content of palladium metal is respectively 0.5% and 1%, palladium catalyst I also contains 0.2% iron, raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, dimethyl oxalate and unreacted CO; Reaction effluent I and methyl alcohol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the dimethyl oxalate product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and methyl nitrite is 1.5: 1, and temperature of reaction is 140 ℃, and reaction velocity is 4000 hours
-1, reaction pressure is 0.05MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place methyl alcohol, NO and oxygen is 3: 1: 0.23,40 ℃ of temperature of reaction, and reaction contact time is 5 seconds, reaction pressure is-0.01MPa.The 3rd reaction zone operational condition: 140 ℃ of temperature of reaction, reaction velocity are 3000 hours
-1, reaction pressure is 0.05MPa.Its reaction result is: CO per pass conversion 86.3%, the selectivity of dimethyl oxalate are 99.6%.
[comparative example 1]
According to identical catalyzer, condition and the reaction raw materials of embodiment 3 first reaction zones, just there is not subsequent reaction zone, do not separate and middle methyl alcohol and the oxygen of replenishing, its reaction result is as follows: CO per pass conversion 40.3%, the selectivity of dimethyl oxalate are 95.8%.
[comparative example 2]
According to identical catalyzer, condition and the reaction raw materials of embodiment 7 first reaction zones, just there is not subsequent reaction zone, do not separate and middle methyl alcohol and the oxygen of replenishing, its reaction result is as follows: CO per pass conversion 58.3%, the selectivity of dimethyl oxalate are 96.1%.
Claims (3)
1. the method for a CO coupling producing oxalic ester may further comprise the steps:
Be raw material with CO and methyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I is carrier with the silicon oxide, palladium catalyst II is carrier with the aluminum oxide, is benchmark with the vehicle weight, and the weight content of palladium metal is respectively 0.2% and 0.8%, raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, dimethyl oxalate and unreacted CO; Reaction effluent I and methyl alcohol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the dimethyl oxalate product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and methyl nitrite is 1.5: 1, and temperature of reaction is 140 ℃, and reaction velocity is 2000 hours
-1, reaction pressure is 0.02MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place methyl alcohol, NO and oxygen is 5: 1: 0.18,70 ℃ of temperature of reaction, and reaction contact time is 8 seconds, reaction pressure is a 0.02MPa; The 3rd reaction zone operational condition: 150 ℃ of temperature of reaction, reaction velocity are 5000 hours
-1, reaction pressure is 0.02MPa; Its reaction result is: CO per pass conversion 83.4%, the selectivity of dimethyl oxalate are 99.3%.
2. the method for a CO coupling producing oxalic ester may further comprise the steps:
Be raw material with CO and methyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I is carrier with the ZSM-5 molecular sieve, silica alumina ratio in the wherein said molecular sieve 800: 1, palladium catalyst II is carrier with the αYang Hualv, be benchmark with the vehicle weight, the weight content of palladium metal is respectively 0.3% and 1.5%, raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, dimethyl oxalate and unreacted CO; Reaction effluent I and methyl alcohol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the dimethyl oxalate product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and methyl nitrite is 3: 1, and temperature of reaction is 160 ℃, and reaction velocity is 5000 hours
-1, reaction pressure is 0.1MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place methyl alcohol, NO and oxygen is 20: 1: 0.24,50 ℃ of temperature of reaction, and reaction contact time is 60 seconds, reaction pressure is 0.02MPa; The 3rd reaction zone operational condition: 140 ℃ of temperature of reaction, reaction velocity are 3000 hours
-1, reaction pressure is 0.3MPa; Its reaction result is: CO per pass conversion 51.4%, the selectivity of dimethyl oxalate are 99.5%.
3. the method for a CO coupling producing oxalic ester may further comprise the steps:
Be raw material with CO and methyl nitrite, wherein, load palladium catalyst I and palladium catalyst II in reactor I and the reactor II respectively, wherein palladium catalyst I is carrier with the αYang Hualv, palladium catalyst II also is carrier with the αYang Hualv, be benchmark with the vehicle weight, the weight content of palladium metal is respectively 0.5% and 1%, palladium catalyst I also contains 0.2% iron, raw material at first enters in first reaction zone and contacts with palladium-containing catalyst I, generates the reaction effluent I that contains NO, dimethyl oxalate and unreacted CO; Reaction effluent I and methyl alcohol and oxygen enter second reaction zone reaction back formation reaction effluent II, and reaction effluent II obtains liquid phase effluent III and gas phase effluent IV through separating; Gas phase effluent IV enters in the 3rd reaction zone and contacts with palladium-containing catalyst II, generates the reaction effluent V that contains barkite; Liquid phase effluent III obtains the dimethyl oxalate product with reaction effluent V after separating; Wherein the mol ratio of first reaction zone operational condition: the CO and methyl nitrite is 1.5: 1, and temperature of reaction is 140 ℃, and reaction velocity is 4000 hours
-1, reaction pressure is 0.05MPa; The second reaction zone operational condition: the mol ratio of reactor inlet place methyl alcohol, NO and oxygen is 3: 1: 0.23,40 ℃ of temperature of reaction, and reaction contact time is 5 seconds, reaction pressure is-0.01MPa; The 3rd reaction zone operational condition: 140 ℃ of temperature of reaction, reaction velocity are 3000 hours
-1, reaction pressure is 0.05MPa; Its reaction result is: CO per pass conversion 86.3%, the selectivity of dimethyl oxalate are 99.6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101468966A CN102219676B (en) | 2010-04-15 | 2010-04-15 | Method for preparing oxalate by CO coupling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101468966A CN102219676B (en) | 2010-04-15 | 2010-04-15 | Method for preparing oxalate by CO coupling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102219676A CN102219676A (en) | 2011-10-19 |
| CN102219676B true CN102219676B (en) | 2013-09-18 |
Family
ID=44776410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101468966A Active CN102219676B (en) | 2010-04-15 | 2010-04-15 | Method for preparing oxalate by CO coupling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102219676B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892819B (en) * | 2017-02-20 | 2019-06-21 | 宁波中科远东催化工程技术有限公司 | A kind of method of CO synthesizing dimethyl oxalate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461909A (en) * | 1980-08-26 | 1984-07-24 | Ube Industries, Ltd. | Process for continuously preparing a diester of oxalic acid |
| CN101143821A (en) * | 2007-10-23 | 2008-03-19 | 天津大学 | Method for preparing diethyl oxalate by coupling CO |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
-
2010
- 2010-04-15 CN CN2010101468966A patent/CN102219676B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461909A (en) * | 1980-08-26 | 1984-07-24 | Ube Industries, Ltd. | Process for continuously preparing a diester of oxalic acid |
| CN101143821A (en) * | 2007-10-23 | 2008-03-19 | 天津大学 | Method for preparing diethyl oxalate by coupling CO |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102219676A (en) | 2011-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475472B (en) | Method for preparing oxalate by coupling reaction of CO in gaseous phase | |
| CN101492370B (en) | Method for producing oxalic ester with CO coupling | |
| CN101475473B (en) | Method for preparing oxalate by coupling reaction of CO | |
| CN101475474B (en) | Method for preparing oxalate by CO conjugation | |
| CN102649735B (en) | Method for producing oxalate through carbon monoxide gas phase-coupled catalytic reaction | |
| CN101993343B (en) | Multi-stage synthesis method of ethylene glycol | |
| CN102219679B (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN101993365B (en) | Method for producing oxalic ester by CO coupling | |
| CN101993363B (en) | Method for preparing oxalic ester by CO coupling | |
| CN102219676B (en) | Method for preparing oxalate by CO coupling | |
| CN102649057A (en) | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) | |
| CN101993364B (en) | Method for producing oxalic ester by gas phase CO coupling | |
| CN101993375B (en) | Method for producing C1-C4 alkyl nitrites | |
| CN102219682A (en) | Method for preparing oxalic ester by CO coupling | |
| CN102219678B (en) | Starting-up method for producing oxalic acid ester with CO | |
| CN102649730B (en) | Method for producing oxalate through carbon monoxide coupling | |
| CN101993374A (en) | Method for preparing C1-C4 alkyl nitrites | |
| CN102649731B (en) | Method for producing oxalate through CO gas phase coupling | |
| CN102649082B (en) | Method for enhancing activity of catalyst for preparing oxalic ester from CO | |
| CN102649728B (en) | Method for producing oxalate through gas-phase reaction of carbon monoxide | |
| CN102219681B (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN102219677A (en) | Method for producing oxalate by coupling carbon monoxide(CO) | |
| CN102219675B (en) | Method for producing oxalic ester by CO coupling | |
| CN102649729A (en) | Method for producing oxalate through CO gas phase coupled catalytic reaction | |
| CN102276458A (en) | Method for producing oxalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |