CN101993364A - Method for producing oxalic ester by gas phase CO coupling - Google Patents
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Abstract
The invention relates to a method for producing oxalic ester by gas phase CO coupling, which mainly solves the technical problems of low oxygen removal rate of raw materials, low selectivity of target products and low space-time yield of the oxalic ester in the prior art. The method comprises the following steps: (a) firstly, a CO gas raw material containing oxygen and NO gas enter a deoxidizing reactor and contact with a molecular sieve catalyst, and the oxygen in the raw material reacts with the NO to generate a gas phase effluent I containing NO2, unreacted NO and CO; (b) the gas phase effluent I and nitrous acid ester enter a coupling reactor and contact with a palladium-containing catalyst to react to generate an effluent II containing the oxalic ester; and (c) the effluent II of the oxalic ester is separated to obtain the oxalic ester product and a gas phase effluent III containing nitrogen oxides, wherein the mol ratio of the NO to oxygen in the CO gas raw material containing the oxygen in the step (a) is 4-100:1. By using the technical scheme, the problems are better solved and the method can be used for the industrial production for increasing the yield of the oxalic ester.
Description
Technical field
The present invention relates to a kind of CO gas phase coupling and produce the method for barkite, particularly about the CO raw material that contains oxygen earlier with NO reaction deoxygenation after again with the method for methyl nitrite or ethyl nitrite coupling production dimethyl oxalate 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 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 0.5MP, temperature is 80 ℃～150 ℃.
As everyone knows, carbon monoxide can be from the various gas mixtures that contain carbon monoxide separation and Extraction, the industrial unstripped gas that can be used for separating carbon monoxide comprises: the tail gas of synthetic gas, water-gas, semi-water gas and Steel Plant, calcium carbide factory and yellow phosphorus factory that Sweet natural gas and oil transform etc.It is pressure swing adsorption process that existing CO separates the main method of purifying, China has many companies to develop transformation fractionation by adsorption carbon monoxide new technology, especially Kai Fa high-efficiency adsorbent, carbon monoxide there are high loading capacity and selectivity, can solve a difficult problem of from the high unstripped gas of nitrogen or methane content, isolating high-purity carbon monooxide, can design and build up large-scale carbon monoxide tripping device.However, by this technology isolated carbon monoxide from synthetic gas, under the prerequisite of taking into account the carbon monoxide yield, generally the content of its hydrogen can reach more than 1%.Follow-up CO coupling reaction catalyst is active to be reduced and the existence that studies show that hydrogen can cause, can't carry out until reaction, do not advise that generally speaking hydrogen content is higher than 10ppm among the CO, therefore, with selectivity oxidizing carbon monoxide dehydrogenation technology is the important component part of CO route synthesis of oxalate technology, but the problem that this technology is brought is to have introduced oxygen when hydrogen is removed again, follow-up CO coupling reaction catalyst is active to be reduced and the existence of oxygen can cause equally, can't carry out until reaction, the oxygen concentration that should control generally speaking in the raw material is not higher than 5ppm, although the oxygen among the CO also can be eliminated by oxidative esterification reaction, but it is big that the problem of bringing is facility investment, the flow process complexity, difficulty maximizes.For this reason, the new deoxy technology of exploitation is significant.
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, do not mention the purity of CO among the present invention, to whether containing oxygen in the raw material and this processing way not being mentioned yet.
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, but this patent do not relate under the industrial application background, contains the technical scheme and the reaction result of oxygen condition.
Summary of the invention
Technical problem to be solved by this invention be existed in the document in the past the feed oxygen decreasing ratio low, the low and low technical problem of barkite space-time yield of purpose selectivity of product, the method that provides a kind of new CO gas phase coupling to produce barkite.This method has feed oxygen decreasing ratio height, the high and high advantage of barkite space-time yield of purpose selectivity of product.
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 CO gas phase coupling is produced the method for barkite, comprises the steps:
A) the CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, contacts with molecular sieve catalyst, and oxygen and NO react in the raw material, generates to contain NO
2, unreacted NO and CO gas phase effluent I;
B) gas phase effluent I and nitrous acid ester enter in the coupler reactor, contact with palladium-containing catalyst, and reaction generates the effluent II that contains barkite;
C) the effluent II of barkite obtains the barkite product and contains the gas phase effluent III of oxynitride after separating;
Wherein, NO is 4～100: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen in the step a).
The reaction conditions of deoxidation reactor is in the technique scheme: temperature of reaction is 10～180 ℃, reaction pressure is-0.08～1.5MPa, reaction contact time is 0.1～50 second, NO is 4.5～50: 1 with the mol ratio preferable range that contains oxygen in the CO gas raw material of oxygen, and more preferably scope is 4.5～30: 1; Optimizing reaction conditions is: temperature of reaction is 50～160 ℃, and more preferably scope is 80～150, and reaction pressure is-0.05～1.0MPa, and reaction contact time is 0.2～30 second.Deoxidation reactor filling molecular sieve catalyst preferred version is selected from least a among ZSM-5, β-molecular sieve, y-zeolite or the MCM-22, and its Si/Al mol ratio preferable range is 10～500: 1; Molecular sieve catalyst more preferably scheme is selected from ZSM-5, and its Si/Al mol ratio more preferably scope is 30～200: 1.
The reaction conditions of coupler reactor is in the technique scheme: the coupler reactor temperature of reaction is 80～160 ℃, and reaction contact time is 0.5～50 second, and reaction pressure is-0.08～1.5MPa, and the mol ratio of CO and nitrous acid ester is: 1～5: 1.The preferred reaction conditions of coupler reactor is: temperature of reaction is 90～150 ℃, and reaction contact time is 0.5～30 second, and reaction pressure is 0.01～1.0MPa, and the mol ratio of CO and nitrous acid ester is: 1.1～3: 1.
To be selected from at least a in silicon oxide, aluminum oxide or the molecular sieve be carrier to the scheme of the carrier of palladium-containing catalyst 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 0.01～1% with catalyst weight, and preferable range is 0.02～0.6%.Catalyzer need add different auxiliary agents, the auxiliary agent preferred version is selected from least a in basic metal, alkaline-earth metal or the transition metal element compound, in its consumption of simple substance is 0.01～10% of catalyst weight, auxiliary agent more preferably scheme is selected from least a in K, Mg, Ba, Zr, V, Mn, Fe, Sn, Ni, Cu, La or the Ce compound, is 0.01～8% of catalyst weight in its consumption of simple substance.Auxiliary agent most preferably scheme is selected from least a in K, Fe, Ce or the Sn compound, in its consumption of simple substance more preferably scope be 0.05～6% of catalyst weight.Activity of such catalysts component and auxiliary element composition are distributed in the carrier shell, present the eggshell state structure of high dispersive.
Nitrous acid ester is selected from methyl nitrite or ethyl nitrite in the technique scheme, preferably from methyl nitrite.The CO gas raw material that contains oxygen, its oxygen volume content is 0.0001～10%, oxygen volume content preferable range is 0.01～8%.
Studies show that in CO and nitrous acid ester coupling reaction process, entering to have oxygen to exist in the raw material of coupler reactor, or the content of oxygen should be lower than 5ppm, otherwise in reaction process, conversion of raw material, the stability of product selectivity and catalyzer all significantly reduce.By introducing NO, it is fast to make full use of NO and oxygen speed of reaction on molecular sieve catalyst among the present invention, and reaction activity is low, and reaction thoroughly, the advantage that the oxygen decreasing ratio is high significantly reduces oxygen content in the raw material, can satisfy the requirement of subsequent production barkite to feed oxygen content.Simultaneously, the mol ratio of NO and oxygen in the strict control raw material among the present invention can ensure the NO and the NO of reaction generation
2Mol ratio be greater than 1: 1, thereby provide useful assurance for recycling of reaction end gas generates barkite.In addition, oxygenous CO raw material can mix with nitrous acid ester after the NO reaction and directly enters coupler reactor among the present invention, and does not need significantly to have reduced equipment size through the oxidative esterification reaction elimination again, has optimized flow process.
Adopt technical scheme of the present invention, allow the CO gas raw material that contains oxygen at first enter deoxidation reactor with NO gas, contact with molecular sieve catalyst, oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO the gas phase effluent, enter in the coupler reactor with nitrous acid ester afterwards, contact with palladium-containing catalyst, reaction generates the effluent that contains barkite, wherein the temperature of reaction of deoxidation reactor is 50～120 ℃, reaction pressure is 0.01～1.0MPa, and reaction contact time is 0.5～30 second, and NO is 4.5～30: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor temperature of reaction is 90～150 ℃, reaction contact time is 0.5～30 second, reaction pressure is 0.01～1.0MPa, the mol ratio of CO and nitrous acid ester is: 1.1～3: under 1 the condition, oxygen can be removed to below the 5ppm in the raw material, and the selectivity of barkite is the highest can be greater than 98%, the space-time yield of barkite greater than 600 grams/(rise. hour), the stability of catalyzer obtained better technical effect greater than 1000 hours.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
The CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, is that 20: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in the coupler reactor, and (its weight consists of: 0.45%Pd+0.40%K+0.22%Fe/ α-Al with palladium-containing catalyst
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains the gas phase effluent III of oxynitride after separating; Wherein, contain that the carrier of oxygen volume concentrations is 8% in the CO gas raw material of oxygen, the operational condition of deoxidation reactor is: temperature of reaction is 20 ℃, and reaction pressure is-0.05MPa, the residence time is 30 seconds, and NO is 4.5: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor operational condition is: temperature of reaction is 120 ℃, and reaction contact time is 30 seconds, and reaction pressure is-0.05MPa that the mol ratio of CO and methyl nitrite is: 1.2: 1.Its result is: oxygen is removed to 3ppm in the raw material, and the selectivity of dimethyl oxalate is 99.1%, the space-time yield of dimethyl oxalate be 900 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours does not have the inactivation sign.
[embodiment 2]
The CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, is that 100: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in the coupler reactor, and (its weight consists of: 0.17%Pd+0.12%Fe/ α-Al with palladium-containing catalyst
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains the gas phase effluent III of oxynitride after separating; Wherein, contain that the carrier of oxygen volume concentrations is 5% in the CO gas raw material of oxygen, the operational condition of deoxidation reactor is: temperature of reaction is 50 ℃, and reaction pressure is 0.01MPa, the residence time is 20 seconds, and NO is 6: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor operational condition is: temperature of reaction is 90 ℃, and reaction contact time is 15 seconds, and reaction pressure is 0.01MPa, and the mol ratio of CO and methyl nitrite is: 2: 1.Its result is: oxygen is removed to 2ppm in the raw material, and the selectivity of dimethyl oxalate is 98.8%, the space-time yield of dimethyl oxalate be 705 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours does not have the inactivation sign.
[embodiment 3]
The CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, is that 200: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in the coupler reactor, and (its weight consists of: 0.34%Pd+1.0%K+0.46%Mn/ α-Al with palladium-containing catalyst
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains the gas phase effluent III of oxynitride after separating; Wherein, contain that the carrier of oxygen volume concentrations is 1% in the CO gas raw material of oxygen, the operational condition of deoxidation reactor is: temperature of reaction is 80 ℃, and reaction pressure is 0.2MPa, the residence time is 30 seconds, and NO is 10: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor operational condition is: temperature of reaction is 100 ℃, and reaction contact time is 9 seconds, and reaction pressure is 0.2MPa, and the mol ratio of CO and methyl nitrite is: 3: 1.Its result is: oxygen is removed to 0 in the raw material, and the selectivity of dimethyl oxalate is 98.6%, the space-time yield of dimethyl oxalate be 840 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours does not have the inactivation sign.
[embodiment 4]
The CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, is that 500: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in the coupler reactor, and (its weight consists of: 0.11%Pd+0.6%Ba+0.2%Fe/ α-Al with palladium-containing catalyst
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains the gas phase effluent III of oxynitride after separating; Wherein, contain that the carrier of oxygen volume concentrations is 0.4% in the CO gas raw material of oxygen, the operational condition of deoxidation reactor is: temperature of reaction is 160 ℃, and reaction pressure is 0.5MPa, the residence time is 10 seconds, and NO is 8: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor operational condition is: temperature of reaction is 140 ℃, and reaction contact time is 2 seconds, and reaction pressure is 0.5MPa, and the mol ratio of CO and methyl nitrite is: 1.2: 1.Its result is: oxygen is removed to 1ppm in the raw material, and the selectivity of dimethyl oxalate is 99.1%, the space-time yield of dimethyl oxalate be 120 grams/(rise. hour) 98.5%.Catalyzer carries out stability test in 1000 hours does not have the inactivation sign.
[embodiment 5]
The CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, is that 200: 1 y-zeolite catalyzer contacts with the Si/Al mol ratio, and oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in the coupler reactor, and (its weight consists of: 0.8%Pd+10%Ce+0.003%Zr/TiO with palladium-containing catalyst
2) contact, reaction generates the effluent II that contains dimethyl oxalate; The effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains the gas phase effluent III of oxynitride after separating; Wherein, contain that the carrier of oxygen volume concentrations is 0.03% in the CO gas raw material of oxygen, the operational condition of deoxidation reactor is: temperature of reaction is 121 ℃, and reaction pressure is 1MPa, the residence time is 3 seconds, and NO is 20: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor operational condition is: temperature of reaction is 160 ℃, and reaction contact time is 1 second, and reaction pressure is 1MPa, and the mol ratio of CO and methyl nitrite is: 1.5: 1.Its result is: oxygen is removed to 0 in the raw material, and the selectivity of dimethyl oxalate is 98.2%, the space-time yield of dimethyl oxalate be 1020 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours does not have the inactivation sign.
[embodiment 6]
The CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, is that β-molecular sieve catalyst of 80: 1 contacts with the Si/Al mol ratio, and oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in the coupler reactor, and (its weight consists of: 0.6%Pd+0.2%Cu+0.08%Fe/99.11% α-Al with palladium-containing catalyst
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains the gas phase effluent III of oxynitride after separating; Wherein, contain that the carrier of oxygen volume concentrations is 1% in the CO gas raw material of oxygen, the operational condition of deoxidation reactor is: temperature of reaction is 100 ℃, and reaction pressure is a normal pressure, the residence time is 0.5 second, and NO is 14: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor operational condition is: temperature of reaction is 120 ℃, and reaction contact time is 3 seconds, and reaction pressure is a normal pressure, and the mol ratio of CO and methyl nitrite is: 2: 1.Its result is: oxygen is removed to 1ppm in the raw material, and the selectivity of dimethyl oxalate is 98.8%, the space-time yield of dimethyl oxalate be 860 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours does not have the inactivation sign.
[embodiment 7]
The CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, is that β-molecular sieve catalyst of 100: 1 contacts with the Si/Al mol ratio, and oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and ethyl nitrite enter in the coupler reactor, and (its weight consists of: 0.2%Pd+0.40%Mg+0.22%Fe/ α-Al with palladium-containing catalyst
2O
3) contact, reaction generates the effluent II that contains oxalic acid diethyl ester; The effluent II of oxalic acid diethyl ester obtains the oxalic acid diethyl ester product and contains the gas phase effluent III of oxynitride after separating; Wherein, contain that the carrier of oxygen volume concentrations is 0.008% in the CO gas raw material of oxygen, the operational condition of deoxidation reactor is: temperature of reaction is 130 ℃, and reaction pressure is 0.2MPa, the residence time is 5 seconds, and NO is 45: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor operational condition is: temperature of reaction is 120 ℃, and reaction contact time is 5 seconds, and reaction pressure is 0.2MPa, and the mol ratio of CO and ethyl nitrite is: 1.3: 1.Its result is: oxygen is removed to 0 in the raw material, and the selectivity of oxalic acid diethyl ester is 98.8%, the space-time yield of oxalic acid diethyl ester be 1130 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours does not have the inactivation sign.
[embodiment 8]
The CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, is that 80: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in the coupler reactor, and (its weight consists of: 0.4%Pd+0.20%La+0.31%Fe/ α-Al with palladium-containing catalyst
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains the gas phase effluent III of oxynitride after separating; Wherein, contain that the carrier of oxygen volume concentrations is 2% in the CO gas raw material of oxygen, the operational condition of deoxidation reactor is: temperature of reaction is 140 ℃, and reaction pressure is 0.2MPa, the residence time is 5 seconds, and NO is 30: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor operational condition is: temperature of reaction is 130 ℃, and reaction contact time is 5 seconds, and reaction pressure is 0.2MPa, and the mol ratio of CO and methyl nitrite is: 1.3: 1.Its result is: oxygen is removed to 0 in the raw material, and the selectivity of dimethyl oxalate is 98.9%, the space-time yield of dimethyl oxalate be 1300 grams/(rise. hour), catalyzer carries out stability test in 1000 hours does not have the inactivation sign.
[embodiment 9]
The CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, is that 150: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and oxygen and NO react in the raw material, generate to contain NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in the coupler reactor, and (its weight consists of: 0.23%Pd+5%Bi+0.08%Fe/ α-Al with palladium-containing catalyst
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains the gas phase effluent III of oxynitride after separating; Wherein, contain that the carrier of oxygen volume concentrations is 0.2% in the CO gas raw material of oxygen, the operational condition of deoxidation reactor is: temperature of reaction is 120 ℃, and reaction pressure is a normal pressure, the residence time is 1 second, and NO is 80: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen; The coupler reactor operational condition is: temperature of reaction is 130 ℃, and reaction contact time is 3 seconds, and reaction pressure is a normal pressure, and the mol ratio of CO and methyl nitrite is: 1.2: 1.Its result is: oxygen is removed to 0ppm in the raw material, and the selectivity of dimethyl oxalate is 97.8%, the space-time yield of dimethyl oxalate be 860 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours does not have the inactivation sign.
[comparative example 1]
According to embodiment 8 identical catalyzer, condition and reaction raw materials, CO oxygen is not handled, its reaction result is as follows: the selectivity of dimethyl oxalate is 88.9%, the space-time yield of dimethyl oxalate be 500 grams/(rise. hour), catalyzer carries out 300 hours stability inactivation.
Claims (10)
1. the method that the CO gas phase coupling is produced barkite comprises the steps:
A) the CO gas raw material that contains oxygen at first enters deoxidation reactor with NO gas, contacts with molecular sieve catalyst, and oxygen and NO react in the raw material, generates to contain NO
2, unreacted NO and CO gas phase effluent I;
B) gas phase effluent I and nitrous acid ester enter in the coupler reactor, contact with palladium-containing catalyst, and reaction generates the effluent II that contains barkite;
C) the effluent II of barkite obtains the barkite product and contains the gas phase effluent III of oxynitride after separating;
Wherein, NO is 4～100: 1 with the mol ratio that contains oxygen in the CO gas raw material of oxygen in the step a).
2. produce the method for barkite according to the described CO gas phase coupling of claim 1, the temperature of reaction that it is characterized in that deoxidation reactor is 10～180 ℃, reaction pressure is-0.08～1.5MPa, reaction contact time is 0.1～50 second, and NO is 4.5～50: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen.
3. produce the method for barkite according to the described CO gas phase coupling of claim 2, the temperature of reaction that it is characterized in that deoxidation reactor is 50～160 ℃, reaction pressure is-0.05～1.0MPa, reaction contact time is 0.2～30 second, and NO is 4.5～30: 1 with the mol ratio that contains the oxygen in the CO gas raw material of oxygen.
4. produce the method for barkite according to the described CO gas phase coupling of claim 1, it is characterized in that the coupler reactor temperature of reaction is 80～160 ℃, reaction contact time is 0.5～50 second, and reaction pressure is-0.08～1.5MPa, and the mol ratio of CO and nitrous acid ester is: 1～5: 1.
5. produce the method for barkite according to the described CO gas phase coupling of claim 4, it is characterized in that the coupler reactor temperature of reaction is 90～150 ℃, reaction contact time is 0.5～30 second, and reaction pressure is 0.01～1.0MPa, and the mol ratio of CO and nitrous acid ester is: 1.1～3: 1.
6. produce the method for barkite according to the described CO gas phase coupling of claim 1, 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 catalyst weight, the weight percent of palladium is 0.01～1%; Molecular sieve catalyst is selected from least a among ZSM-5, β-molecular sieve, y-zeolite or the MCM-22, and its Si/Al mol ratio is 10～500: 1.
7. the method for producing barkite according to the described CO gas phase coupling of claim 6 is characterized in that palladium-containing catalyst is carrier with the aluminum oxide, and in catalyst weight, the weight percent of palladium is 0.02～0.6%; Molecular sieve catalyst is selected from ZSM-5, and its Si/Al mol ratio is 30～200: 1.
8. the method for producing barkite according to the described CO gas phase coupling of claim 1 is characterized in that nitrous acid ester is selected from methyl nitrite or ethyl nitrite.
9. according to the method for the described CO gas phase coupling production of claim 1 barkite, it is characterized in that containing the CO gas raw material of oxygen, its oxygen volume content is 0.0001～10%.
10. according to the method for the described CO gas phase coupling production of claim 9 barkite, it is characterized in that containing the CO gas raw material of oxygen, its oxygen volume content is 0.01～8%.
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| CN2009100578434A CN101993364B (en) | 2009-08-31 | 2009-08-31 | Method for producing oxalic ester by gas phase CO coupling |
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| CN104941633A (en) * | 2015-06-01 | 2015-09-30 | 江苏金聚合金材料有限公司 | One-pot preparation and use of multicomponent composite carrier |
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| CN112441922B (en) * | 2019-09-02 | 2023-04-07 | 中国石油化工股份有限公司 | Method for preparing oxalate through CO oxidative coupling, catalyst and preparation method thereof |
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