CN102219681A - Method for producing oxalic acid ester through CO gas phase coupling - Google Patents
Method for producing oxalic acid ester through CO gas phase coupling Download PDFInfo
- Publication number
- CN102219681A CN102219681A CN2010101470330A CN201010147033A CN102219681A CN 102219681 A CN102219681 A CN 102219681A CN 2010101470330 A CN2010101470330 A CN 2010101470330A CN 201010147033 A CN201010147033 A CN 201010147033A CN 102219681 A CN102219681 A CN 102219681A
- Authority
- CN
- China
- Prior art keywords
- reaction
- effluent
- acid ester
- pressure
- oxynitride
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for producing oxalic acid ester through CO gas phase coupling. The use of the method is aimed to mainly solving the technical problems of low nitric oxide utilization ratio and low conversion rate of raw materials in the prior art. A technical scheme is adopted as follows: the method comprises the following steps of: (a) firstly, leading gas containing CO and nitrite ester into a coupling reactor, then contacting with a palladium-containing catalyst, and reacting to produce reaction effluent I containing nitric oxide and the oxalic acid ester; (b) separating the reaction effluent I to obtain reaction effluent II containing the oxalic acid ester and reaction effluent III containing nitric oxide, and leading the reaction effluent III into an oxidation and esterification reactor and reacting with oxygen and C1-C4 monohydric alcohol, thus producing gas effluent IV containing nitrite ester; and (c) separating the reaction effluent II to obtain an oxalic acid ester product, wherein the reaction pressure of the oxidation and esterification reactor is lower than the pressure in the coupling reactor, thus better solving the problems of low nitric oxide utilization ratio and the low conversion rate of the raw materials and being used for industrial production of the oxalic acid ester.
Description
Technical field
The present invention relates to a kind of method of CO gas phase coupling producing oxalic ester, particularly the method for producing dimethyl oxalate or oxalic acid diethyl ester about vapor phase process CO and methyl nitrite or ethyl nitrite reaction.
Background technology
Barkite is important Organic Chemicals, is used for fine chemistry industry in a large number and prepares 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 is separated and can be got 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 crucial industrial chemicals 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 0.5MPa, 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 crucial strategic importance.At present, by carbon monoxide oxidative coupling method synthesis of oxalate 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, and obtained bigger progress.
Although above-mentioned numerous research institution has obtained technically than much progress, technology itself still remains further perfect and develops, and especially improves aspects such as oxynitride utilization ratio how, all needs further research and raising.
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, this invention is on the basis of lab scale research in early stage, is that background is carried out with the industrial production, and the continuous operation examination is amplified in mould examination and the pilot scale finished under the industrial operation condition.But how this technology does not mention technology such as more effective raising oxynitride utilization ratio.
Document CN 95116136.9 discloses the catalyzer of the synthetic usefulness of a kind of barkite, selects for use Zr 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.Equally, how this technology does not relate to technology such as more effective raising oxynitride utilization ratio.
Summary of the invention
Technical problem to be solved by this invention is to exist the oxynitride utilization ratio low in the prior art, and the technical problem that feed stock conversion is low provides a kind of method of new CO gas phase coupling producing oxalic ester.This method has oxynitride utilization ratio height, the advantage that feed stock conversion 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 gas phase coupling producing oxalic ester may further comprise the steps:
A) gas that contains CO and nitrous acid ester at first enters coupler reactor, contacts with palladium-containing catalyst, and reaction generates the reaction effluent I that contains oxynitride and barkite;
B) reaction effluent I obtains containing the reaction effluent II and the reaction effluent III that contains oxynitride of barkite after separating, and the reaction effluent III that contains oxynitride enters the oxidative esterification reaction device, with oxygen, C
1～C
4Monohydroxy-alcohol reaction, generate the gaseous effluent IV that contains nitrous acid ester;
C) the reaction effluent II that contains barkite obtains the barkite product after separating;
Wherein, the reaction pressure of oxidative esterification reaction device is lower than the pressure of coupler reactor, and the reaction pressure of oxidative esterification reaction device is-0.09～0MPa, and the reaction pressure of coupler reactor is 0.001～1.0MPa.
The coupler reactor operational condition is in the technique scheme: temperature of reaction is 60～180 ℃, and the reaction volume air speed is 500～10000 hours
-1, reaction pressure is 0.005～1.0MPa, the mol ratio of CO and nitrous acid ester is 1～3: 1; Coupler reactor preferred operations condition is: temperature of reaction is 80～160 ℃, and the reaction volume air speed is 800～6000 hours
-1, reaction pressure is 0.01～0.8MPa, the mol ratio of CO and nitrous acid ester is 1～2.5: 1.
Oxidative esterification reaction device operational condition in the technique scheme: 0～80 ℃ of temperature of reaction, reaction contact time are 0.1～100 second, and reaction pressure is-0.08～0MPa, oxynitride: O
2: C
1～C
4The mol ratio of monohydroxy-alcohol be 1: 0.10～0.25: 1～10; Oxidative esterification reaction device operation conditions optimization is: 10～60 ℃ of temperature of reaction, reaction contact time are 0.5～50 second, reaction pressure is-0.08～-0.01MPa, oxynitride: O
2: C
1～C
4The mol ratio of monohydroxy-alcohol be 1: 0.15～0.25: 1～5.
The carrier of palladium-containing catalyst is selected from least a in aluminum oxide, silicon oxide, the molecular sieve in the technique scheme, and preferred version is selected from α-Al
2O
3, θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3Or at least a in the molecular sieve, more preferably scheme is selected from α-Al
2O
3, the shape of carrier can be made different shapes as required, and as cylindric, spherical, sheet, tubular, cellular or Raschig ring etc., but sphere is reasonable selection, and its diameter is preferably 1～6 millimeter, so that industrial application.The content of palladium counts 0.02～1.5% with vehicle weight, and preferable range is 0.05～1%, and more preferably scope is 0.1～0.8%.
C in the technique scheme
1～C
4The monohydroxy-alcohol preferred version be selected from methyl alcohol, ethanol or its mixture, more preferably scheme is selected from methyl alcohol.
Among the present invention: adopt the continuous cyclical operation of coupler reactor and oxidative esterification (regeneration) reactor to realize that the oxidative esterification reaction of CO linked reaction and NO generates carrying out continuously of nitrous acid ester reaction, guarantee the self-enclosed circulation of reaction process, whole process is non-pollution discharge almost.In addition, as everyone knows, in the oxidative esterification reaction process of NO, except the main reaction that generates nitrous acid ester, also can generate the side reaction of nitric acid, the generation of side reaction has not only aggravated the corrosion of equipment, but also has reduced the utilization ratio of raw material oxynitride (NO), thereby cause the increase of system's oxynitride additional amount, the increase of material consumption and energy consumption.A large amount of studies show that, in the NO oxidative esterification reaction process, generates the side reaction and the N of nitric acid
4O
2Generation closely related, N
4O
2Concentration high more, the probability that generates by product such as nitric acid is just big more, and deep discovering, the pressure of oxidative esterification reaction system and N
4O
2Generation closely related, pressure is high more, N
4O
2The easy more generation of formation reaction, pressure is low more, to generating N
4O
2The reaction effect of drawing up obvious more.But research finds that also in the CO coupling reaction process, suitable pressure can effectively improve conversion of raw material and product selectivity under existing.The present invention adopts the lower working pressure in oxynitride (NO) oxidative esterification reaction unit for this reason, and the high relatively reaction pressure in CO linked reaction unit, both effectively prevented the generation of oxynitride oxidative esterification unit side reaction, improved the utilization ratio of oxynitride, simultaneously, guaranteed that again unitary conversion of raw material of CO linked reaction and product selectivity improve.
Adopt technical scheme of the present invention, in the coupler reactor operational condition be: temperature of reaction is 80～160 ℃, and the reaction volume air speed is 800～6000 hours
-1, reaction pressure is 0.01～0.8MPa, the mol ratio of CO and nitrous acid ester is: 1～2.5: and 1, catalyzer is for being the palladium catalyst of carrier with the aluminum oxide, the content of palladium counts 0.1～0.8% with catalyst weight; Oxidative esterification reaction device operational condition: 10～60 ℃ of temperature of reaction, reaction contact time are 0.5～50 second, reaction pressure is-0.08～-0.01MPa, oxynitride: O
2: C
1～C
4The mol ratio of monohydroxy-alcohol be 1: 0.15～0.25: 1～5, C wherein
1～C
4Monohydroxy-alcohol be selected under methyl alcohol or the alcoholic acid condition, the utilization ratio of oxynitride can reach 99.8%, obtains better technical effect.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Preparation of Catalyst:
Iron nitrate is dissolved in the water, is heated to 80 ℃, the vacuum rotary dipping is at α-Al of 5 millimeters
2O
3On the bead, then in 120 ℃ of dryings 4 hours.Repone K and ammonium palladic chloride are dissolved in the water respectively, making its pH value with the HCl regulator solution is about 4, then this solution is heated to 80 ℃, be impregnated into once more on the carrier, then in 140 ℃ of dryings 4 hours, then 450 ℃ of roastings 4 hours, reduce to room temperature, obtaining required catalyzer, is benchmark (as follows) with the vehicle weight, and its weight consists of: 0.45%Pd+0.40%K+0.22%Fe/ α-Al
2O
3
Take by weighing the above-mentioned catalyzer that makes 10 grams, the diameter of packing into is in 18 millimeters the tubular type coupler reactor, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature was reduced to temperature of reaction and is fed intake after 3 hour.
To contain CO and at first enter coupler reactor with the gas of methyl nitrite and contact with palladium-containing catalyst, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separating, the reaction effluent III that obtains containing the reaction effluent II of dimethyl oxalate and contain oxynitride, the reaction effluent III that contains oxynitride enters the oxidative esterification reaction unit, with oxygen, methyl alcohol reaction, generates the gaseous effluent IV that contains methyl nitrite; The reaction effluent II that contains dimethyl oxalate obtains the dimethyl oxalate product after separating.Wherein, the coupler reactor reaction conditions is: 90 ℃ of temperature of reaction, reaction volume air speed are 1000 hours
-1, reaction pressure is 0.2MPa, the mol ratio of CO and methyl nitrite is: 1.2: 1; Oxidative esterification reaction device operational condition: 40 ℃ of temperature of reaction, be 0.5 second duration of contact, reaction pressure is-0.02MPa NO: O
2: the mol ratio of methyl alcohol is 1: 0.2: 1, and its effect is: the NO utilization ratio is 99.3%, CO per pass conversion 70%, and the selectivity of dimethyl oxalate is 99.2%.
[embodiment 2]
Make according to embodiment 1 identical method and to consist of 0.17%Pd+0.12%Fe/ α-Al
2O
3Required catalyzer.
Take by weighing the above-mentioned catalyzer that makes 10 grams, the diameter of packing into is in 18 millimeters the tubular type coupler reactor, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature was reduced to temperature of reaction and is fed intake after 3 hour.
To contain CO and at first enter coupler reactor with the gas of methyl nitrite and contact with palladium-containing catalyst, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separating, the reaction effluent III that obtains containing the reaction effluent II of dimethyl oxalate and contain oxynitride, the reaction effluent III that contains oxynitride enters the oxidative esterification reaction unit, with oxygen, methyl alcohol reaction, generation contains the gaseous effluent IV of methyl nitrite, gaseous effluent IV with return coupler reactor after CO mixes and proceed reaction; The reaction effluent II that contains dimethyl oxalate obtains the dimethyl oxalate product after separating.Wherein, the coupler reactor reaction conditions is: 120 ℃ of temperature of reaction, reaction volume air speed are 2000 hours
-1, reaction pressure is 0.5MPa, the mol ratio of CO and methyl nitrite is 1.5: 1; Oxidative esterification reaction device operational condition: 70 ℃ of temperature of reaction, be 5 seconds duration of contact, reaction pressure is-0.08MPa NO: O
2: the mol ratio of methyl alcohol is 1: 0.1: 3, and its effect is: the NO utilization ratio is 99.1%, CO per pass conversion 60%, and the selectivity of dimethyl oxalate is 98.5%.
[embodiment 3]
Make according to embodiment 1 identical method and to consist of 0.34%Pd+1.0%K+0.46%Mn/ α-Al
2O
3Required catalyzer.
Take by weighing the above-mentioned catalyzer that makes 10 grams, the diameter of packing into is in 18 millimeters the tubular type coupler reactor, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature was reduced to temperature of reaction and is fed intake after 3 hour.
To contain CO and at first enter coupler reactor with the gas of methyl nitrite and contact with palladium-containing catalyst, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separating, the reaction effluent III that obtains containing the reaction effluent II of dimethyl oxalate and contain oxynitride, the reaction effluent III that contains oxynitride enters the oxidative esterification reaction unit, with oxygen, methyl alcohol reaction, generation contains the gaseous effluent IV of methyl nitrite, gaseous effluent IV with return coupler reactor after CO mixes and proceed reaction; The reaction effluent II that contains dimethyl oxalate obtains the dimethyl oxalate product after separating.Wherein, the coupler reactor reaction conditions is: 160 ℃ of temperature of reaction, reaction volume air speed are 4000 hours
-1, reaction pressure is 0.8MPa, the mol ratio of CO and methyl nitrite is 3: 1; Oxidative esterification reaction device operational condition: 25 ℃ of temperature of reaction, be 80 seconds duration of contact, reaction pressure is-0.03MPa NO: O
2: the mol ratio of methyl alcohol is 1: 0.2: 8, and its effect is: the NO utilization ratio is 99.0%, CO per pass conversion 27%, and the selectivity of dimethyl oxalate is 98.2%.
[embodiment 4]
Make according to embodiment 1 identical method and to consist of the magnesian required catalyzer of 0.11%Pd+0.6%Ba+0.2%Fe/.
Take by weighing the above-mentioned catalyzer that makes 10 grams, the diameter of packing into is in 18 millimeters the tubular type coupler reactor, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature was reduced to temperature of reaction and is fed intake after 3 hour.
To contain CO and at first enter coupler reactor with the gas of methyl nitrite and contact with palladium-containing catalyst, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separating, the reaction effluent III that obtains containing the reaction effluent II of dimethyl oxalate and contain oxynitride, the reaction effluent III that contains oxynitride enters the oxidative esterification reaction unit, with oxygen, methyl alcohol reaction, generation contains the gaseous effluent IV of methyl nitrite, gaseous effluent IV with return coupler reactor after CO mixes and proceed reaction; The reaction effluent II that contains dimethyl oxalate obtains the dimethyl oxalate product after separating.Wherein, the coupler reactor reaction conditions is: 140 ℃ of temperature of reaction, reaction volume air speed are 3000 hours
-1, reaction pressure is 0.4MPa, the mol ratio of CO and methyl nitrite is 1.3: 1; Oxidative esterification reaction device operational condition: 45 ℃ of temperature of reaction, reaction contact time are 20 seconds, and reaction pressure is-0.05MPa NO: O
2: the mol ratio of methyl alcohol is 1: 0.15: 1.4, and its effect is: the NO utilization ratio is 99.1%, CO per pass conversion 70%, and the selectivity of dimethyl oxalate is 99.4%.
[embodiment 5]
Make according to embodiment 1 identical method and to consist of 0.8%Pd/TiO
2Required catalyzer.
Take by weighing the above-mentioned catalyzer that makes 10 grams, the diameter of packing into is in 18 millimeters the tubular type coupler reactor, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature was reduced to temperature of reaction and is fed intake after 3 hour.
To contain CO and at first enter coupler reactor with the gas of methyl nitrite and contact with palladium-containing catalyst, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separating, the reaction effluent III that obtains containing the reaction effluent II of dimethyl oxalate and contain oxynitride, the reaction effluent III that contains oxynitride enters the oxidative esterification reaction unit, with oxygen, methyl alcohol reaction, generation contains the gaseous effluent IV of methyl nitrite, gaseous effluent IV with return coupler reactor after CO mixes and proceed reaction; The reaction effluent II that contains dimethyl oxalate obtains the dimethyl oxalate product after separating.Wherein, the coupler reactor reaction conditions is: 160 ℃ of temperature of reaction, reaction volume air speed are 8000 hours
-1, reaction pressure is a normal pressure, the mol ratio of CO and methyl nitrite is 2: 1; Oxidative esterification reaction device operational condition: 50 ℃ of temperature of reaction, reaction contact time are 10 seconds, and reaction pressure is-0.03MPa NO: O
2: the mol ratio of methyl alcohol is 1: 0.23: 10, and its effect is: the NO utilization ratio is 99.3%, CO per pass conversion 47%, and the selectivity of dimethyl oxalate is 98.91%.
[embodiment 6]
Make according to embodiment 1 identical method and to consist of 0.3%Pd+10%Ce+0.507%Fe/ α-Al
2O
3Required catalyzer.
Take by weighing the above-mentioned catalyzer that makes 10 grams, the diameter of packing into is in 18 millimeters the tubular type coupler reactor, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature was reduced to temperature of reaction and is fed intake after 3 hour.
To contain CO and at first enter coupler reactor with the raw material of ethyl nitrite and contact with palladium-containing catalyst, reaction generates the reaction effluent I that contains oxynitride and oxalic acid diethyl ester; Reaction effluent I is after separating, the reaction effluent III that obtains containing the reaction effluent II of oxalic acid diethyl ester and contain oxynitride, the reaction effluent III that contains oxynitride enters the oxidative esterification reaction unit, with oxygen, ethanol synthesis, generation contains the effluent IV of ethyl nitrite, effluent IV with return coupler reactor after CO mixes and proceed reaction; The reaction effluent II that contains oxalic acid diethyl ester obtains the oxalic acid diethyl ester product after separating.Wherein, the coupler reactor reaction conditions is: 100 ℃ of temperature of reaction, reaction volume air speed are 800 hours
-1, reaction pressure is a normal pressure, the mol ratio of CO and ethyl nitrite is 2: 1; Oxidative esterification reaction device operational condition: 30 ℃ of temperature of reaction, reaction contact time are 10 seconds, and reaction pressure is-0.08MPa NO: O
2: the alcoholic acid mol ratio is 1: 0.13: 5, and its effect is: the NO utilization ratio is 99.7%, CO per pass conversion 45%, and the selectivity of oxalic acid diethyl ester is 98.7%.
[embodiment 7]
Make according to embodiment 1 identical method and to consist of 0.6%Pd+0.2%Cu+0.08%Fe/ α-Al
2O
3Required catalyzer.
Take by weighing the above-mentioned catalyzer that makes 10 grams, the diameter of packing into is in 18 millimeters the tubular type coupler reactor, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature was reduced to temperature of reaction and is fed intake after 3 hour.
To contain CO and at first enter coupler reactor with the raw material of propyl nitrite and contact with palladium-containing catalyst, reaction generates the reaction effluent I that contains oxynitride and dipropyl oxalate; Reaction effluent I is after separating, the reaction effluent III that obtains containing the reaction effluent II of dipropyl oxalate and contain oxynitride, the reaction effluent III that contains oxynitride enters the oxidative esterification reaction unit, with oxygen, propyl alcohol reaction, generation contains the effluent IV of propyl nitrite, effluent IV with return coupler reactor after CO mixes and proceed reaction; The reaction effluent II that contains dipropyl oxalate obtains the dipropyl oxalate product after separating.Wherein, the coupler reactor reaction conditions is: 80 ℃ of temperature of reaction, reaction volume air speed are 500 hours
-1, reaction pressure is 0.4MPa, the mol ratio of CO and propyl nitrite is 1.5: 1; Oxidative esterification reaction device operational condition: 30 ℃ of temperature of reaction, reaction contact time are 10 seconds, and reaction pressure is-0.05MPa NO: O
2: the mol ratio of propyl alcohol is that its effect is: the NO utilization ratio is 99.6% under 1: 0.23: 10 the condition, CO per pass conversion 40%, and the selectivity of dipropyl oxalate is 98.5%.
[embodiment 8]
Make the required catalyzer that consists of 0.05%Pd+0.015%La according to embodiment 1 identical method.
Take by weighing the above-mentioned catalyzer that makes 10 grams, the diameter of packing into is in 18 millimeters the tubular type coupler reactor, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature was reduced to temperature of reaction and is fed intake after 3 hour.
To contain CO and at first enter coupler reactor with the gas of methyl nitrite and contact with palladium-containing catalyst, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separating, the reaction effluent III that obtains containing the reaction effluent II of dimethyl oxalate and contain oxynitride, the reaction effluent III that contains oxynitride enters the oxidative esterification reaction unit, with oxygen, methyl alcohol reaction, generation contains the gaseous effluent IV of methyl nitrite, gaseous effluent IV with return coupler reactor after CO mixes and proceed reaction; The reaction effluent II that contains dimethyl oxalate obtains the dimethyl oxalate product after separating.Wherein, the coupler reactor reaction conditions is: 150 ℃ of temperature of reaction, reaction volume air speed are 5000 hours
-1, reaction pressure is a normal pressure, the mol ratio of CO and methyl nitrite is 1.3: 1; Oxidative esterification reaction device operational condition: 40 ℃ of temperature of reaction, reaction contact time are 30 seconds, and reaction pressure is-0.06MPa NO: O
2: the mol ratio of methyl alcohol is 1: 0.18: 10, and its effect is: the NO utilization ratio is 99.8%, CO per pass conversion 65%, and the selectivity of dimethyl oxalate is 98.8%.
[embodiment 9]
Make the required catalyzer that consists of 0.5%Pd+0.01%Zn according to embodiment 1 identical method.
Take by weighing the above-mentioned catalyzer that makes 10 grams, the diameter of packing into is in 18 millimeters the tubular type coupler reactor, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature was reduced to temperature of reaction and is fed intake after 3 hour.
To contain CO and at first enter coupler reactor with the gas of methyl nitrite and contact with palladium-containing catalyst, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separating, the reaction effluent III that obtains containing the reaction effluent II of dimethyl oxalate and contain oxynitride, the reaction effluent III that contains oxynitride enters the oxidative esterification reaction unit, with oxygen, methyl alcohol reaction, generation contains the gaseous effluent IV of methyl nitrite, gaseous effluent IV with return coupler reactor after CO mixes and proceed reaction; The reaction effluent II that contains dimethyl oxalate obtains the dimethyl oxalate product after separating.Wherein, the coupler reactor reaction conditions is: 130 ℃ of temperature of reaction, reaction volume air speed are 2000 hours
-1, reaction pressure is a normal pressure, the mol ratio of CO and methyl nitrite is 1.3: 1; Oxidative esterification reaction device operational condition: 10 ℃ of temperature of reaction, reaction contact time are 30 seconds, and reaction pressure is-0.08MPa NO: O
2: the mol ratio of methyl alcohol is 1: 0.18: 10, and its effect is: the NO utilization ratio is 99.5%, CO per pass conversion 65%, and the selectivity of dimethyl oxalate is 99.5%.
[comparative example 1]
Employing is with embodiment 4 identical catalyzer and condition, just NO oxidative esterification unit and the unitary reaction pressure of CO linked reaction are 0.4MPa, its reaction result is: the NO utilization ratio is 93.1%, CO per pass conversion 63%, and the selectivity of dimethyl oxalate is 96.2%.
Claims (7)
1. the method for a CO gas phase coupling producing oxalic ester may further comprise the steps:
A) gas that contains CO and nitrous acid ester at first enters coupler reactor, contacts with palladium-containing catalyst, and reaction generates the reaction effluent I that contains oxynitride and barkite;
B) reaction effluent I obtains containing the reaction effluent II and the reaction effluent III that contains oxynitride of barkite after separating, and the reaction effluent III that contains oxynitride enters the oxidative esterification reaction device, with oxygen, C
1～C
4Monohydroxy-alcohol reaction, generate the gaseous effluent IV that contains nitrous acid ester;
C) the reaction effluent II that contains barkite obtains the barkite product after separating;
Wherein, the reaction pressure of oxidative esterification reaction device is lower than the pressure of coupler reactor, and the reaction pressure of oxidative esterification reaction device is-0.09～0MPa, and the reaction pressure of coupler reactor is 0.001～1.0MPa.
2. according to the method for the described CO gas phase coupling of claim 1 producing oxalic ester, it is characterized in that the coupler reactor operational condition is: temperature of reaction is 60～180 ℃, and the reaction volume air speed is 500～10000 hours
-1, reaction pressure is 0.005～1.0MPa, the mol ratio of CO and nitrous acid ester is 1～3: 1; Oxidative esterification reaction device operational condition: 0～80 ℃ of temperature of reaction, reaction contact time are 0.1～100 second, and reaction pressure is-0.08～0MPa, oxynitride: O
2: C
1～C
4The mol ratio of monohydroxy-alcohol be 1: 0.10～0.25: 1～10.
3. according to the method for the described CO gas phase coupling of claim 2 producing oxalic ester, it is characterized in that the coupler reactor operational condition is: temperature of reaction is 80～160 ℃, and the reaction volume air speed is 800～6000 hours
-1, reaction pressure is 0.01～0.8MPa, the mol ratio of CO and nitrous acid ester is 1～2.5: 1; Oxidative esterification reaction device operational condition: 10～60 ℃ of temperature of reaction, reaction contact time are 0.5～50 second, reaction pressure is-0.08～-0.01MPa, oxynitride: O
2: C
1～C
4The mol ratio of monohydroxy-alcohol be 1: 0.15～0.25: 1～5.
4. according to the method for the described CO gas phase coupling of claim 1 producing oxalic ester, the carrier that it is characterized in that palladium-containing catalyst is selected from least a in aluminum oxide, silicon oxide, the molecular sieve, and the content of palladium counts 0.02～1.5% with vehicle weight.
5. according to the method for the described CO gas phase coupling of claim 4 producing oxalic ester, it is characterized in that the carrier of palladium-containing catalyst is selected from aluminum oxide, the content of palladium is in vehicle weight 0.05～1%.
6. according to the method for the described CO gas phase coupling of claim 5 producing oxalic ester, it is characterized in that the carrier of palladium-containing catalyst is selected from Alpha-alumina, the content of palladium is in vehicle weight 0.1～0.8%.
7. according to the method for the described CO gas phase coupling of claim 1 producing oxalic ester, it is characterized in that C
1～C
4Monohydroxy-alcohol be selected from methyl alcohol, ethanol or its mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010147033.0A CN102219681B (en) | 2010-04-15 | 2010-04-15 | Method for producing oxalic acid ester through CO gas phase coupling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010147033.0A CN102219681B (en) | 2010-04-15 | 2010-04-15 | Method for producing oxalic acid ester through CO gas phase coupling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102219681A true CN102219681A (en) | 2011-10-19 |
| CN102219681B CN102219681B (en) | 2014-03-05 |
Family
ID=44776415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010147033.0A Active CN102219681B (en) | 2010-04-15 | 2010-04-15 | Method for producing oxalic acid ester through CO gas phase coupling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102219681B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649755A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing dimethyl carbonate by CO gaseous-phase coupling |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149047A (en) * | 1996-09-18 | 1997-05-07 | 天津大学 | Diethyl oxalate by gas phase CO link-coupled regeneration catalyzing circulation |
| 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 CN201010147033.0A patent/CN102219681B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149047A (en) * | 1996-09-18 | 1997-05-07 | 天津大学 | Diethyl oxalate by gas phase CO link-coupled regeneration catalyzing circulation |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649755A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing dimethyl carbonate by CO gaseous-phase coupling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102219681B (en) | 2014-03-05 |
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 | |
| CN101993344A (en) | Method for preparing ethylene glycol from synthesis gas | |
| CN102219680B (en) | Method for preparing oxalic ester by CO gas-phase process | |
| CN101993366B (en) | Method for preparing oxalate by using CO gaseous phase process | |
| CN102649735B (en) | Method for producing oxalate through carbon monoxide gas phase-coupled catalytic reaction | |
| CN101993363B (en) | Method for preparing oxalic ester by CO coupling | |
| CN102649057B (en) | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) | |
| CN101993365B (en) | Method for producing oxalic ester by CO coupling | |
| CN102219679B (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN101475474A (en) | Method for preparing oxalate coupling reaction of CO | |
| CN102219681B (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN102649731B (en) | Method for producing oxalate through CO gas phase coupling | |
| CN101993341B (en) | Method for producing glycol through hydrogenation of oxalic ester | |
| CN102649082B (en) | Method for enhancing activity of catalyst for preparing oxalic ester from CO | |
| CN102649730B (en) | Method for producing oxalate through carbon monoxide coupling | |
| CN102649734B (en) | Method for producing oxalate through catalytic coupling reaction of carbon monoxide | |
| CN101993375A (en) | Method for producing C1-C4 alkyl nitrites | |
| CN102219678B (en) | Starting-up method for producing oxalic acid ester with CO | |
| CN102649728B (en) | Method for producing oxalate through gas-phase reaction of carbon monoxide | |
| CN102219676B (en) | Method for preparing oxalate by CO coupling | |
| CN102649729A (en) | Method for producing oxalate through CO gas phase coupled catalytic reaction | |
| CN102219682A (en) | Method for preparing oxalic ester by CO coupling | |
| CN102649738A (en) | Method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |